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1. Packing Biomolecules into Sierpiński Triangles with Global Organizational Chirality

Author: Na Li, Jie Li, Hao Tang, Zhen Xu, Chao Li, Ruoning Li, Yajie Zhang, Xue Zhang, Yongfeng Wang, Ziyong Shen, Surfaces, Interfaces et Nano-Objets (CEMES-SINanO), Centre d'élaboration de matériaux et d'études structurales (CEMES), Université Toulouse III - Paul Sabatier (UT3), Université Fédérale Toulouse Midi-Pyrénées-Université Fédérale Toulouse Midi-Pyrénées-Centre National de la Recherche Scientifique (CNRS)-Institut de Chimie de Toulouse (ICT-FR 2599), Institut National Polytechnique (Toulouse) (Toulouse INP), Université Fédérale Toulouse Midi-Pyrénées-Université Fédérale Toulouse Midi-Pyrénées-Centre National de la Recherche Scientifique (CNRS)-Institut de Recherche pour le Développement (IRD)-Université Toulouse III - Paul Sabatier (UT3), Université Fédérale Toulouse Midi-Pyrénées-Institut de Chimie du CNRS (INC)-Institut National Polytechnique (Toulouse) (Toulouse INP), Université Fédérale Toulouse Midi-Pyrénées-Centre National de la Recherche Scientifique (CNRS)-Institut de Recherche pour le Développement (IRD)-Institut de Chimie du CNRS (INC)-Institut National des Sciences Appliquées - Toulouse (INSA Toulouse), Institut National des Sciences Appliquées (INSA)-Institut National des Sciences Appliquées (INSA)-Université Toulouse III - Paul Sabatier (UT3), Institut National des Sciences Appliquées (INSA)-Institut National des Sciences Appliquées (INSA), Institut National des Sciences Appliquées - Toulouse (INSA Toulouse), Institut National des Sciences Appliquées (INSA)-Université de Toulouse (UT)-Institut National des Sciences Appliquées (INSA)-Université de Toulouse (UT)-Institut de Chimie de Toulouse (ICT), Institut de Recherche pour le Développement (IRD)-Université Toulouse III - Paul Sabatier (UT3), Université de Toulouse (UT)-Université de Toulouse (UT)-Institut de Chimie du CNRS (INC)-Centre National de la Recherche Scientifique (CNRS)-Institut National Polytechnique (Toulouse) (Toulouse INP), Université de Toulouse (UT)-Institut de Recherche pour le Développement (IRD)-Université Toulouse III - Paul Sabatier (UT3), Université de Toulouse (UT)-Institut de Chimie du CNRS (INC)-Centre National de la Recherche Scientifique (CNRS)-Institut National Polytechnique (Toulouse) (Toulouse INP), Université de Toulouse (UT)-Centre National de la Recherche Scientifique (CNRS)-Institut National des Sciences Appliquées - Toulouse (INSA Toulouse), and Université de Toulouse (UT)-Centre National de la Recherche Scientifique (CNRS)
Subjects: Silver, Pyridines, 02 engineering and technology, 010402 general chemistry, 01 natural sciences, Biochemistry, Catalysis, law.invention, Colloid and Surface Chemistry, Fractal, law, Benzene Derivatives, Molecule, Density Functional Theory, Radioisotopes, chemistry.chemical_classification, Biomolecule, Intermolecular force, Tryptophan, Hydrogen Bonding, Stereoisomerism, General Chemistry, 021001 nanoscience & nanotechnology, 0104 chemical sciences, Sierpinski triangle, Fractals, Models, Chemical, chemistry, Chemical physics, [PHYS.COND.CM-GEN]Physics [physics]/Condensed Matter [cond-mat]/Other [cond-mat.other], Density functional theory, Adsorption, Scanning tunneling microscope, 0210 nano-technology, Chirality (chemistry)
Abstract: Fractals are found in nature and play important roles in biological functions. However, it is challenging to controllably prepare biomolecule fractals. In this study, a series of Sierpiński triangles with global organizational chirality is successfully constructed by the coassembly of l-tryptophan and 1,3-bi(4-pyridyl)benzene molecules on Ag(111). The chirality is switched when replacing l-tryptophan by d-tryptophan. The fractal structures are characterized by low-temperature scanning tunneling microscopy at the single-molecule level. Density functional theory calculations reveal that intermolecular hydrogen bonds stabilize the Sierpiński triangles.
Published: 2021

2. Unraveling the Capacitive Charge Storage Mechanism of Nitrogen-Doped Porous Carbons by EQCM and ssNMR

Author: En Zhang, Yih-Chyng Wu, Hui Shao, Vytautas Klimavicius, Hanyue Zhang, Pierre-Louis Taberna, Julia Grothe, Gerd Buntkowsky, Fei Xu, Patrice Simon, Stefan Kaskel, Publica, Technische Universität Dresden = Dresden University of Technology (TU Dresden), Centre interuniversitaire de recherche et d'ingenierie des matériaux (CIRIMAT), Université Toulouse III - Paul Sabatier (UT3), Université de Toulouse (UT)-Université de Toulouse (UT)-Institut de Chimie du CNRS (INC)-Centre National de la Recherche Scientifique (CNRS)-Institut National Polytechnique (Toulouse) (Toulouse INP), Université de Toulouse (UT), Réseau sur le stockage électrochimique de l'énergie (RS2E), Aix Marseille Université (AMU)-Université Toulouse III - Paul Sabatier (UT3), Université de Toulouse (UT)-Université de Toulouse (UT)-Université de Haute-Alsace (UHA) Mulhouse - Colmar (Université de Haute-Alsace (UHA))-Collège de France (CdF (institution))-Université de Picardie Jules Verne (UPJV)-Ecole Nationale Supérieure de Chimie de Paris - Chimie ParisTech-PSL (ENSCP), Université Paris sciences et lettres (PSL)-Université Paris sciences et lettres (PSL)-Université de Pau et des Pays de l'Adour (UPPA)-Institut de Chimie du CNRS (INC)-Sorbonne Université (SU)-Centre National de la Recherche Scientifique (CNRS)-Institut National Polytechnique (Toulouse) (Toulouse INP), Université de Toulouse (UT)-Institut polytechnique de Grenoble - Grenoble Institute of Technology (Grenoble INP ), Université Grenoble Alpes (UGA)-Université Grenoble Alpes (UGA)-Nantes Université (Nantes Univ)-Université de Montpellier (UM)-Ecole Nationale Supérieure de Chimie de Montpellier (ENSCM), Université de Montpellier (UM), Vilnius University [Vilnius], Technische Universität Darmstadt - Technical University of Darmstadt (TU Darmstadt), Fraunhofer Institute Material and Beam Technology [Dresden] (Fraunhofer IWS), Fraunhofer (Fraunhofer-Gesellschaft), and German Science Foundation (Deutsche Forschungsgemeinschaft, grants no. KA 1698/27-1)
Subjects: Ions, X-ray photoelectron spectroscopy, Magnetic Resonance Spectroscopy, Nitrogen, [CHIM.MATE]Chemical Sciences/Material chemistry, General Chemistry, Lithium, Biochemistry, Catalysis, Carbon, Colloid and Surface Chemistry, Cations, Electrical properties, Quartz Crystal Microbalance Techniques, [CHIM.OTHE]Chemical Sciences/Other, Electrodes, Porosity, Nuclear magnetic resonance spectroscopy
Abstract: International audience; Fundamental understanding of ion electroadsorption processes in porous electrodes on a molecular level provides important guidelines for next-generation energy storage devices like electric double layer capacitors (EDLCs). Porous carbons functionalized by heteroatoms show enhanced capacitive performance, but the underlying mechanism is still elusive, due to the lack of reliable tools to precisely identify multiple N species and establish clear structure property relations. Here, we use advanced analytical techniques such as lowtemperature solid-state NMR (ssNMR) and electrochemical quartz crystal microbalance (EQCM) to relate the complex nitrogen functionalities to the charging mechanisms and capacitive performance. For the first time, it is demonstrated at a molecular level that N-doping strongly influences the electroadsorption mechanism in EDLCs. Without N-doping, anion (SO 4 2−) adsorption−desorption dominates the charging mechanism, whereas after doping, Li + electroadsorption plays a key role. With the help of EQCM, it is demonstrated that SO 4 2− is strongly immobilized on the Ndoped surface, leaving Li + as the main charge carrier. The smaller size and higher concentration of Li + compared to SO 4 2− benefit a higher capacitance. Amine/amide N is responsible for high capacitance, but surprisingly the pyridinic, pyrrolic, and graphitic N groups have no significant influence. 2D 1 H-15 N NMR spectroscopy indicates that the conversion from pyridinium to pyrrolic N gives rise to a slightly decreased capacitance. This work not only demonstrates ssNMR as a powerful tool for surface chemistry characterization of electrode materials but also uncovers the related charging mechanism by EQCM, paving the way toward a comprehensive picture of EDLC chemistry.
Published: 2022

3. Heterometallic Clusters with Multiple Rare Earth Metal–Transition Metal Bonding

Author: Penglong Wang, Yue Zhao, Kaiying Shi, Iskander Douair, Genfeng Feng, Congqing Zhu, Laurent Maron, Laboratoire de physique et chimie des nano-objets (LPCNO), Institut National des Sciences Appliquées - Toulouse (INSA Toulouse), Institut National des Sciences Appliquées (INSA)-Université de Toulouse (UT)-Institut National des Sciences Appliquées (INSA)-Université de Toulouse (UT)-Institut de Chimie de Toulouse (ICT), Institut de Recherche pour le Développement (IRD)-Université Toulouse III - Paul Sabatier (UT3), Université de Toulouse (UT)-Université de Toulouse (UT)-Institut de Chimie du CNRS (INC)-Centre National de la Recherche Scientifique (CNRS)-Institut National Polytechnique (Toulouse) (Toulouse INP), Université de Toulouse (UT)-Institut de Recherche pour le Développement (IRD)-Université Toulouse III - Paul Sabatier (UT3), Université de Toulouse (UT)-Institut de Chimie du CNRS (INC)-Centre National de la Recherche Scientifique (CNRS)-Institut National Polytechnique (Toulouse) (Toulouse INP), Université de Toulouse (UT)-Fédération de recherche « Matière et interactions » (FeRMI), Institut National des Sciences Appliquées (INSA)-Université de Toulouse (UT)-Institut National des Sciences Appliquées (INSA)-Université de Toulouse (UT)-Université Toulouse III - Paul Sabatier (UT3), Université de Toulouse (UT)-Centre National de la Recherche Scientifique (CNRS)-Centre National de la Recherche Scientifique (CNRS), Nanjing Normal Univ, Key Lab Virtual Geog Environm, Minist Educ, Nanjing 210023, Peoples R China, National Natural Science Foundation of China [21772088, 91961116], Natural Science Foundation of Jiangsu Province [BK20200302], Fundamental Research Funds for the Central Universities [14380216], and Programs for high-level entrepreneurial and innovative talents introduction of Jiangsu Province (group program)
Subjects: Magnetism, Chemistry, Molecular cluster, Rare earth, General Chemistry, 010402 general chemistry, 01 natural sciences, Biochemistry, Catalysis, 0104 chemical sciences, Metal, Crystallography, Colloid and Surface Chemistry, Transition metal, X-ray photoelectron spectroscopy, Oxidation state, visual_art, visual_art.visual_art_medium, Molecule, [PHYS.PHYS.PHYS-CHEM-PH]Physics [physics]/Physics [physics]/Chemical Physics [physics.chem-ph]
Abstract: International audience; Although a series of complexes with rare earth (RE) metal-metal bonds have been reported, complexes which have multiple RE-Rh bonds are unknown. Here we present the identification of the first example of a molecule containing multiple RE-Rh bonds. The complex with multiple Ce-Rh bonds was synthesized by the reduction of a d-f heterometallic molecular cluster Ce{N[((CH2CH2NPPr2)-Pr-i)RhCl(COD)](3)} with excess potassium-graphite. The oxidation state of Ce in 3a appears to be a mixture of Ce(III) and Ce(IV), which was confirmed by X-ray photoelectron spectroscopy, magnetism, and theoretical investigations (DFT and CASSCF). For comparison, the analogous species with multiple La(III)-Rh and Nd(III)-Rh bonds were also constructed. This study provides a possible route for the construction of complexes with multiple RE metal-metal bonds and an investigation of their potential properties and applications.
Published: 2021

4. Cyclic Poly(α-peptoid)s by Lithium bis(trimethylsilyl)amide (LiHMDS)-Mediated Ring-Expansion Polymerization: Simple Access to Bioactive Backbones

Author: Pierre Verhaeghe, Sébastien Lecommandoux, Antoine Tronnet, Marc Since, Jean-Luc Stigliani, Pedro Salas-Ambrosio, Sandra Bourgeade-Delmas, Bruno Dupuy, Amelie Vax, Colin Bonduelle, Team 3 LCPO : Polymer Self-Assembly & Life Sciences, Laboratoire de Chimie des Polymères Organiques (LCPO), Centre National de la Recherche Scientifique (CNRS)-Institut Polytechnique de Bordeaux-Ecole Nationale Supérieure de Chimie, de Biologie et de Physique (ENSCBP)-Université de Bordeaux (UB)-Institut de Chimie du CNRS (INC)-Centre National de la Recherche Scientifique (CNRS)-Institut Polytechnique de Bordeaux-Ecole Nationale Supérieure de Chimie, de Biologie et de Physique (ENSCBP)-Université de Bordeaux (UB)-Institut de Chimie du CNRS (INC), Laboratoire de chimie de coordination (LCC), Institut National Polytechnique (Toulouse) (Toulouse INP), Université Fédérale Toulouse Midi-Pyrénées-Université Fédérale Toulouse Midi-Pyrénées-Université Toulouse III - Paul Sabatier (UT3), Université Fédérale Toulouse Midi-Pyrénées-Institut de Chimie de Toulouse (ICT-FR 2599), Université Fédérale Toulouse Midi-Pyrénées-Université Fédérale Toulouse Midi-Pyrénées-Centre National de la Recherche Scientifique (CNRS)-Institut de Recherche pour le Développement (IRD)-Université Toulouse III - Paul Sabatier (UT3), Université Fédérale Toulouse Midi-Pyrénées-Institut de Chimie du CNRS (INC)-Centre National de la Recherche Scientifique (CNRS)-Institut de Recherche pour le Développement (IRD)-Institut de Chimie du CNRS (INC)-Centre National de la Recherche Scientifique (CNRS), Pathogénèse des Bactéries Anaérobies / Pathogenesis of Bacterial Anaerobes (PBA (U-Pasteur_6)), Institut Pasteur [Paris]-Centre National de la Recherche Scientifique (CNRS)-Université de Paris (UP), Centre d'Etudes et de Recherche sur le Médicament de Normandie (CERMN), Université de Caen Normandie (UNICAEN), Normandie Université (NU)-Normandie Université (NU), Pharmacochimie et Biologie pour le Développement (PHARMA-DEV), Université Toulouse III - Paul Sabatier (UT3), Université Fédérale Toulouse Midi-Pyrénées-Université Fédérale Toulouse Midi-Pyrénées-Institut de Chimie de Toulouse (ICT-FR 2599), Université Fédérale Toulouse Midi-Pyrénées-Institut de Chimie du CNRS (INC)-Institut National Polytechnique (Toulouse) (Toulouse INP), Université Fédérale Toulouse Midi-Pyrénées-Centre National de la Recherche Scientifique (CNRS)-Institut de Recherche pour le Développement (IRD)-Institut de Chimie du CNRS (INC)-Institut de Recherche pour le Développement (IRD), and Université Fédérale Toulouse Midi-Pyrénées
Subjects: Trimethylsilyl Compounds, Cell Survival, Polymers, Lithium bis(trimethylsilyl)amide, Microbial Sensitivity Tests, [CHIM.THER]Chemical Sciences/Medicinal Chemistry, 010402 general chemistry, Ring (chemistry), 01 natural sciences, Biochemistry, Catalysis, Cell Line, Polymerization, Macrocyclic polypeptoids, Peptoids, chemistry.chemical_compound, Colloid and Surface Chemistry, Biological property, Humans, Density Functional Theory, Ring expansion polymerization (REP), chemistry.chemical_classification, Clostridioides difficile, Peptoid, General Chemistry, Polymer, Combinatorial chemistry, 0104 chemical sciences, [CHIM.POLY]Chemical Sciences/Polymers, Monomer, chemistry, Cyclization
Abstract: International audience; Cyclic polymers display unique physicochemical and biological properties. However, their development is often limited by their challenging preparation. In this work, we present a simple route to cyclic poly(α-peptoids) from N-alkylated-N-carboxyanhydrides (NNCA) using LiHMDS promoted ring-expansion polymerization (REP) in DMF. This new method allows the unprecedented use of lysine-like monomers in REP to design bioactive macrocycles bearing pharmaceutical potential against Clostridioides difficile, a bacterium responsible for nosocomial infections.
Published: 2021

5. Scandium-Terminal Boronylphosphinidene Complex

Author: Laurent Maron, Xuebing Leng, Yaofeng Chen, Bin Feng, Li Xiang, Ambre Carpentier, University of Chinese Academy of Sciences [Beijing] (UCAS), Laboratoire de physique et chimie des nano-objets (LPCNO), Institut National des Sciences Appliquées - Toulouse (INSA Toulouse), Institut National des Sciences Appliquées (INSA)-Université de Toulouse (UT)-Institut National des Sciences Appliquées (INSA)-Université de Toulouse (UT)-Institut de Chimie de Toulouse (ICT), Institut de Recherche pour le Développement (IRD)-Université Toulouse III - Paul Sabatier (UT3), Université de Toulouse (UT)-Université de Toulouse (UT)-Institut de Chimie du CNRS (INC)-Centre National de la Recherche Scientifique (CNRS)-Institut National Polytechnique (Toulouse) (Toulouse INP), Université de Toulouse (UT)-Institut de Recherche pour le Développement (IRD)-Université Toulouse III - Paul Sabatier (UT3), Université de Toulouse (UT)-Institut de Chimie du CNRS (INC)-Centre National de la Recherche Scientifique (CNRS)-Institut National Polytechnique (Toulouse) (Toulouse INP), Université de Toulouse (UT)-Fédération de recherche « Matière et interactions » (FeRMI), Institut National des Sciences Appliquées (INSA)-Université de Toulouse (UT)-Institut National des Sciences Appliquées (INSA)-Université de Toulouse (UT)-Université Toulouse III - Paul Sabatier (UT3), Université de Toulouse (UT)-Centre National de la Recherche Scientifique (CNRS)-Centre National de la Recherche Scientifique (CNRS), National Natural Science Foundation of China [21732007, 21890721, 21821002], K. C. Wong Education Foundation, Strategic Priority Research Program of the Chinese Academy of Sciences [XDB20000000], Shanghai Municipal Committee of Science and Technology, Program of Shanghai Academic Research Leader, and Chinese Academy of Sciences President's International Fellowship Initiative
Subjects: chemistry.chemical_element, General Chemistry, Weak interaction, 010402 general chemistry, 01 natural sciences, Biochemistry, Catalysis, 0104 chemical sciences, Bond length, Crystallography, Colloid and Surface Chemistry, chemistry, Nucleophile, Phosphinidene, Reactivity (chemistry), [PHYS.PHYS.PHYS-CHEM-PH]Physics [physics]/Physics [physics]/Chemical Physics [physics.chem-ph], Scandium
Abstract: International audience; The first isolation and structural characterization of a rare-earth metal-terminal imido complex were reported in 2010, but a rare-earth metal-terminal phosphinidene complex is still absent, to date. Herein, we report the synthesis and structure of the first example of a rare-earth-terminal phosphinidene complex, namely the scandium boronylphosphinidene complex. Single-crystal X-ray diffraction shows that the complex has a much shorter Sc-P bond length as compared to that in a related scandium boronylphosphido complex, 2.381(1) angstrom vs 2.564(1) angstrom. DFT calculations indicate the presence of a strong Sc-P pi interaction in this complex, which is in striking contrast to the weak interaction found in the phosphido complex. A preliminary reactivity study demonstrates that the scandium-terminal boronylphosphinidene complex behaves as a nucleophilic phosphinidene complex.
Published: 2021

6. Accessing the +IV Oxidation State in Molecular Complexes of Praseodymium

Author: Farzaneh Fadaei-Tirani, Laurent Maron, Aurélien R. Willauer, Marinella Mazzanti, Ivica Zivkovic, Chad T. Palumbo, Iskander Douair, Ecole Polytechnique Fédérale de Lausanne (EPFL), Laboratoire de physique et chimie des nano-objets (LPCNO), Institut National des Sciences Appliquées - Toulouse (INSA Toulouse), Institut National des Sciences Appliquées (INSA)-Université de Toulouse (UT)-Institut National des Sciences Appliquées (INSA)-Université de Toulouse (UT)-Institut de Chimie de Toulouse (ICT), Institut de Recherche pour le Développement (IRD)-Université Toulouse III - Paul Sabatier (UT3), Université de Toulouse (UT)-Université de Toulouse (UT)-Institut de Chimie du CNRS (INC)-Centre National de la Recherche Scientifique (CNRS)-Institut National Polytechnique (Toulouse) (Toulouse INP), Université de Toulouse (UT)-Institut de Recherche pour le Développement (IRD)-Université Toulouse III - Paul Sabatier (UT3), Université de Toulouse (UT)-Institut de Chimie du CNRS (INC)-Centre National de la Recherche Scientifique (CNRS)-Institut National Polytechnique (Toulouse) (Toulouse INP), Université de Toulouse (UT)-Institut de Recherche sur les Systèmes Atomiques et Moléculaires Complexes (IRSAMC), Université Toulouse III - Paul Sabatier (UT3), and Université de Toulouse (UT)-Université de Toulouse (UT)-Centre National de la Recherche Scientifique (CNRS)-Centre National de la Recherche Scientifique (CNRS)
Subjects: Lanthanide, lanthanide, Praseodymium, chemistry.chemical_element, Terbium, Ate complex, chemistry, 010402 general chemistry, 01 natural sciences, Biochemistry, Catalysis, law.invention, electron-paramagnetic-resonance, Colloid and Surface Chemistry, nitrate, law, Oxidation state, Electron paramagnetic resonance, General Chemistry, 0104 chemical sciences, yttrium, Crystallography, Cerium, ions, [PHYS.PHYS.PHYS-CHEM-PH]Physics [physics]/Physics [physics]/Chemical Physics [physics.chem-ph], Cyclic voltammetry
Abstract: Out of the 14 lanthanide (Ln) ions, molecular complexes of Ln(IV) were known only for cerium and more recently terbium. Here we demonstrate that the +IV oxidation state is also accessible for the large praseodymium (Pr) cation. The oxidation of the tetrakis(triphenysiloxide) Pr(III) ate complex, [KPr(OSiPh3)(4)(THF)(3)], 1-Pr-Ph, with [N(C6H4Br)(3)][SbCl6], affords the Pr(IV) complex [Pr(OSiPh3)(4)(MeCN)(2)], 2-Pr-Ph, which is stable once isolated. The solid state structure, UV-visible spectroscopy, magnetometry, and cyclic voltammetry data along with the DFT computations of the 2-Pr-Ph complex unambiguously confirm the presence of Pr(IV).
Published: 2020

7. Reactivity of Multimetallic Thorium Nitrides Generated by Reduction of Thorium Azides

Author: Fang-Che Hsueh, Luciano Barluzzi, Megan Keener, Thayalan Rajeshkumar, Laurent Maron, Rosario Scopelliti, Marinella Mazzanti, Ecole Polytechnique Fédérale de Lausanne (EPFL), Laboratoire de physique et chimie des nano-objets (LPCNO), Institut National des Sciences Appliquées - Toulouse (INSA Toulouse), Institut National des Sciences Appliquées (INSA)-Université de Toulouse (UT)-Institut National des Sciences Appliquées (INSA)-Université de Toulouse (UT)-Institut de Chimie de Toulouse (ICT), Institut de Recherche pour le Développement (IRD)-Université Toulouse III - Paul Sabatier (UT3), Université de Toulouse (UT)-Université de Toulouse (UT)-Institut de Chimie du CNRS (INC)-Centre National de la Recherche Scientifique (CNRS)-Institut National Polytechnique (Toulouse) (Toulouse INP), Université de Toulouse (UT)-Institut de Recherche pour le Développement (IRD)-Université Toulouse III - Paul Sabatier (UT3), Université de Toulouse (UT)-Institut de Chimie du CNRS (INC)-Centre National de la Recherche Scientifique (CNRS)-Institut National Polytechnique (Toulouse) (Toulouse INP), Université de Toulouse (UT)-Fédération de recherche « Matière et interactions » (FeRMI), Institut National des Sciences Appliquées (INSA)-Université de Toulouse (UT)-Institut National des Sciences Appliquées (INSA)-Université de Toulouse (UT)-Université Toulouse III - Paul Sabatier (UT3), Université de Toulouse (UT)-Centre National de la Recherche Scientifique (CNRS)-Centre National de la Recherche Scientifique (CNRS), Swiss National Science Foundation [178793], and Ecole Polytechnique Federale de Lausanne (EPFL)
Subjects: Colloid and Surface Chemistry, General Chemistry, [PHYS.PHYS.PHYS-CHEM-PH]Physics [physics]/Physics [physics]/Chemical Physics [physics.chem-ph], Biochemistry, Catalysis
Abstract: International audience; Thorium nitrides are likely intermediates in the reported cleavage and functionalization of dinitrogen by molecular thorium complexes and are attractive compounds for the study of multiple bond formation in f-element chemistry, but only one example of thorium nitride isolable from solution was reported. Here, we show that stable multimetallic azide/nitride thorium complexes can be generated by reduction of thorium azide precursors.a route that has failed so far to produce Th nitrides. Once isolated, the thorium azide/nitride clusters, M3Th = N = Th (M = K or Cs), are stable in solutions probably due to the presence of alkali ions capping the nitride, but their synthesis requires a careful control of the reaction conditions (solvent, temperature, nature of precursor, and alkali ion). The nature of the cation plays an important role in generating a nitride product and results in large structural differences with a bent Th = N = Th moiety found in the K-bound nitride as a result of a strong K-nitride interaction and a linear arrangement in the Cs-bound nitride. Reactivity studies demonstrated the ability of Th nitrides to cleave CO in ambient conditions yielding CN-.
Published: 2022

8. Azo-Derived Symmetrical Trithiocarbonate for Unprecedented RAFT Control

Author: Oleksandr Ivanchenko, Sonia Mallet-Ladeira, Stéphane Mazières, Maksym Odnoroh, Mathias Destarac, Marc Guerre, Interactions moléculaires et réactivité chimique et photochimique (IMRCP), Institut de Chimie de Toulouse (ICT), Institut de Recherche pour le Développement (IRD)-Université Toulouse III - Paul Sabatier (UT3), Université de Toulouse (UT)-Université de Toulouse (UT)-Institut de Chimie du CNRS (INC)-Centre National de la Recherche Scientifique (CNRS)-Institut National Polytechnique (Toulouse) (Toulouse INP), Université de Toulouse (UT)-Institut de Recherche pour le Développement (IRD)-Université Toulouse III - Paul Sabatier (UT3), Université de Toulouse (UT)-Institut Ecologie et Environnement (INEE), Centre National de la Recherche Scientifique (CNRS)-Centre National de la Recherche Scientifique (CNRS)-Fédération de Recherche Fluides, Energie, Réacteurs, Matériaux et Transferts (FERMAT), Institut National des Sciences Appliquées - Toulouse (INSA Toulouse), Institut National des Sciences Appliquées (INSA)-Université de Toulouse (UT)-Institut National des Sciences Appliquées (INSA)-Université de Toulouse (UT)-Université Toulouse III - Paul Sabatier (UT3), Université de Toulouse (UT)-Centre National de la Recherche Scientifique (CNRS)-Institut National Polytechnique (Toulouse) (Toulouse INP), Université de Toulouse (UT)-Institut National des Sciences Appliquées - Toulouse (INSA Toulouse), Institut National des Sciences Appliquées (INSA)-Université de Toulouse (UT)-Institut National des Sciences Appliquées (INSA)-Centre National de la Recherche Scientifique (CNRS)-Centre National de la Recherche Scientifique (CNRS), P3R - Polymères de Précision par Procédés Radicalaires (P3R), Institut National des Sciences Appliquées (INSA)-Université de Toulouse (UT)-Institut National des Sciences Appliquées (INSA)-Centre National de la Recherche Scientifique (CNRS)-Centre National de la Recherche Scientifique (CNRS)-Institut de Chimie de Toulouse (ICT), Laboratoire de chimie de coordination (LCC), Université de Toulouse (UT)-Centre National de la Recherche Scientifique (CNRS), and ANR-16-CE29-0014,RAFTSWITCH,Agents de Transfert RAFT Modulables pour la Polymérisation Radicalaire Contrôlée.(2016)
Subjects: Trithiocarbonate, Chemistry, [CHIM.ORGA]Chemical Sciences/Organic chemistry, Radical polymerization, Leaving group, Chain transfer, General Chemistry, Raft, Methacrylate, Biochemistry, Block copolymers, Catalysis, Polymerization, Colloid and Surface Chemistry, [CHIM.POLY]Chemical Sciences/Polymers, Polymer chemistry, Copolymer, Thiol, Thermoplastic elastomer
Abstract: International audience; Bis(2-cyanopropan-2-yl)trithiocarbonate (TTC-bCP) is a new symmetrical trithiocarbonate with the best leaving group ever reported for reversible addition–fragmentation chain transfer (RAFT) polymerization. We propose an elegant route to obtain TTC-bCP starting from 2,2′-azobis(2-methylpropionitrile) (AIBN) as a donor of the 2-cyanopropan-2-yl group. TTC-bCP allowed the preparation of a high-molar-mass (Mn ≈ 135 kg mol–1) methyl methacrylate–n-butyl acrylate–methyl methacrylate triblock copolymer with unprecedented control (D̵ = 1.04) in reversible-deactivation radical polymerization. Rheology measurements of this triblock copolymer showed a typical thermoplastic elastomer behavior with a steady rubbery plateau up to 120 °C.
Published: 2021

9. Nucleophilic Addition to π-Allyl Gold(III) Complexes: Evidence for Direct and Undirect Paths

Author: Yago García-Rodeja, Sonia Mallet-Ladeira, Karinne Miqueu, Didier Bourissou, Pierre Lavedan, Jéssica Rodríguez, Marte Sofie Martinsen Holmsen, E. Daiann Sosa Carrizo, Laboratoire Hétérochimie Fondamentale et Appliquée (LHFA), Université Toulouse III - Paul Sabatier (UT3), Université Fédérale Toulouse Midi-Pyrénées-Université Fédérale Toulouse Midi-Pyrénées-Centre National de la Recherche Scientifique (CNRS)-Institut de Chimie du CNRS (INC)-Institut de Chimie de Toulouse (ICT-FR 2599), Institut National Polytechnique (Toulouse) (Toulouse INP), Université Fédérale Toulouse Midi-Pyrénées-Université Fédérale Toulouse Midi-Pyrénées-Centre National de la Recherche Scientifique (CNRS)-Institut de Recherche pour le Développement (IRD)-Université Toulouse III - Paul Sabatier (UT3), Université Fédérale Toulouse Midi-Pyrénées-Institut de Chimie du CNRS (INC)-Institut National Polytechnique (Toulouse) (Toulouse INP), Université Fédérale Toulouse Midi-Pyrénées-Centre National de la Recherche Scientifique (CNRS)-Institut de Recherche pour le Développement (IRD), Institut des sciences analytiques et de physico-chimie pour l'environnement et les materiaux (IPREM), Université de Pau et des Pays de l'Adour (UPPA)-Institut de Chimie du CNRS (INC)-Centre National de la Recherche Scientifique (CNRS), Institut de Chimie de Toulouse (ICT-FR 2599), Université Fédérale Toulouse Midi-Pyrénées-Institut de Chimie du CNRS (INC), Institut de Chimie de Toulouse (ICT), Institut de Recherche pour le Développement (IRD)-Université Toulouse III - Paul Sabatier (UT3), Université de Toulouse (UT)-Université de Toulouse (UT)-Institut de Chimie du CNRS (INC)-Centre National de la Recherche Scientifique (CNRS)-Institut National Polytechnique (Toulouse) (Toulouse INP), Université de Toulouse (UT)-Institut de Recherche pour le Développement (IRD)-Université Toulouse III - Paul Sabatier (UT3), Université de Toulouse (UT)-Centre National de la Recherche Scientifique (CNRS), Université de Toulouse (UT), and ANR-19-CE07-0037,Gold-III,Chimie de l'or(III)(2019)
Subjects: Allylic rearrangement, 010402 general chemistry, 01 natural sciences, Biochemistry, Medicinal chemistry, Catalysis, Coupling reaction, chemistry.chemical_compound, Colloid and Surface Chemistry, Nucleophile, [CHIM]Chemical Sciences, MECHANISM PATHWAYS, Reactivity (chemistry), Organometallic chemistry, Substitution reaction, Nucleophilic addition, 010405 organic chemistry, Chemistry, Regioselectivity, π-ALLYL COMPLEXES, General Chemistry, DFT CALCULATIONS, 0104 chemical sciences, CROSS-COUPLING REACTIONS, NUCLEOPHILIC ATTACK, GOLD CATALYSIS
Abstract: International audience; π-Allyl complexes play a prominent role in organometallic chemistry and have attracted considerable attention, in particular the π-allyl Pd(II) complexes which are key intermediates in the Tsuji-Trost allylic substitution reaction. Despite the huge interest in π-complexes of gold, π-allyl Au(III) complexes were only authenticated very recently. Herein, we report the reactivity of (P,C)-cyclometalated Au(III) π-allyl complexes toward β-diketo enolates. Behind an apparently trivial outcome, i.e. the formation of the corresponding allylation products, meticulous NMR studies combined with DFT calculations revealed a complex and rich mechanistic picture. Nucleophilic attack can occur at the central and terminal positions of the π-allyl as well as the metal itself. All paths are observed and are actually competitive, whereas addition to the terminal positions largely prevails for Pd(II). Auracyclobutanes and π-alkene Au(I) complexes were authenticated spectroscopically and crystallographically, and Au(III) σ-allyl complexes were unambiguously characterized by multinuclear NMR spectroscopy. Nucleophilic additions to the central position of the π-allyl and to gold are reversible. Over time, the auracyclobutanes and the Au(III) σ-allyl complexes evolve into the π-alkene Au(I) complexes and release the C-allylation products. The relevance of auracyclobutanes in gold-mediated cyclopropanation was demonstrated by inducing C-C coupling with iodine. The molecular orbitals of the π-allyl Au(III) complexes were analyzed in-depth, and the reaction profiles for the addition of β-diketo enolates were thoroughly studied by DFT. Special attention was devoted to the regioselectivity of the nucleophilic attack, but C-C coupling to give the allylation products was also considered to give a complete picture of the reaction progress.
Published: 2021

10. Synergistic Effect of High-Frequency Ultrasound with Cupric Oxide Catalyst Resulting in a Selectivity Switch in Glucose Oxidation under Argon

Author: Yingqiao Wang, Ngoc Han Tran, Duy Quang Dao, Prince Nana Amaniampong, Matthew Sherburne, François Jérôme, Karine De Oliveira Vigier, Quang Thang Trinh, Institut de Chimie des Milieux et Matériaux de Poitiers (IC2MP), Université de Poitiers-Institut national des sciences de l'Univers (INSU - CNRS)-Institut de Chimie du CNRS (INC)-Centre National de la Recherche Scientifique (CNRS), Fédération de recherche INCREASE (INCREASE), Institut des Sciences Moléculaires (ISM), Université Montesquieu - Bordeaux 4-Université Sciences et Technologies - Bordeaux 1 (UB)-École Nationale Supérieure de Chimie et de Physique de Bordeaux (ENSCPB)-Institut de Chimie du CNRS (INC)-Centre National de la Recherche Scientifique (CNRS)-Université Montesquieu - Bordeaux 4-Université Sciences et Technologies - Bordeaux 1 (UB)-École Nationale Supérieure de Chimie et de Physique de Bordeaux (ENSCPB)-Institut de Chimie du CNRS (INC)-Centre National de la Recherche Scientifique (CNRS)-LIttoral ENvironnement et Sociétés (LIENSs), La Rochelle Université (ULR)-Centre National de la Recherche Scientifique (CNRS)-La Rochelle Université (ULR)-Centre National de la Recherche Scientifique (CNRS)-Institut de Chimie des Milieux et Matériaux de Poitiers (IC2MP), Université de Poitiers-Institut national des sciences de l'Univers (INSU - CNRS)-Institut de Chimie du CNRS (INC)-Centre National de la Recherche Scientifique (CNRS)-Université de Poitiers-Institut national des sciences de l'Univers (INSU - CNRS)-Institut de Chimie du CNRS (INC)-Centre National de la Recherche Scientifique (CNRS)-Institut des Sciences Chimiques de Rennes (ISCR), Université de Rennes (UR)-Institut National des Sciences Appliquées - Rennes (INSA Rennes), Institut National des Sciences Appliquées (INSA)-Institut National des Sciences Appliquées (INSA)-Ecole Nationale Supérieure de Chimie de Rennes (ENSCR)-Institut de Chimie du CNRS (INC)-Centre National de la Recherche Scientifique (CNRS)-Université de Rennes (UR)-Institut National des Sciences Appliquées - Rennes (INSA Rennes), Institut National des Sciences Appliquées (INSA)-Institut National des Sciences Appliquées (INSA)-Ecole Nationale Supérieure de Chimie de Rennes (ENSCR)-Centre National de la Recherche Scientifique (CNRS)-Laboratoire de Chimie des Polymères Organiques (LCPO), Université de Bordeaux (UB)-Ecole Nationale Supérieure de Chimie, de Biologie et de Physique (ENSCBP)-Institut Polytechnique de Bordeaux-Institut de Chimie du CNRS (INC)-Centre National de la Recherche Scientifique (CNRS)-Université de Bordeaux (UB)-Ecole Nationale Supérieure de Chimie, de Biologie et de Physique (ENSCBP)-Institut Polytechnique de Bordeaux-Centre National de la Recherche Scientifique (CNRS)-Laboratoire de Génie Chimique (LGC), Université Toulouse III - Paul Sabatier (UT3), Université de Toulouse (UT)-Université de Toulouse (UT)-Centre National de la Recherche Scientifique (CNRS)-Institut National Polytechnique (Toulouse) (Toulouse INP), Université de Toulouse (UT)-Université Toulouse III - Paul Sabatier (UT3), Université de Toulouse (UT)-Unité de recherche sur les Biopolymères, Interactions Assemblages (BIA), Institut National de Recherche pour l’Agriculture, l’Alimentation et l’Environnement (INRAE)-Institut National de Recherche pour l’Agriculture, l’Alimentation et l’Environnement (INRAE)-Centre de recherche sur l'intégration économique et financière (CRIEF), Université de Poitiers-Université de Poitiers, Nanyang Technological University [Singapour], Physicochimie de la Combustion (PC2), Physicochimie des Processus de Combustion et de l’Atmosphère - UMR 8522 (PC2A), Université de Lille-Centre National de la Recherche Scientifique (CNRS)-Université de Lille-Centre National de la Recherche Scientifique (CNRS), National Research Foundation Singapore, Centre National de la Recherche Scientifique, R?gion Nouvelle-Aquitaine, ANR-16-CE07-0003,CELLOPLASM,Clivage de la liaison béta-1,4 glycosidique de la cellulose par plasma atmospherique non-thermique: mécanisme et application pour la production d'alkylglycosides(2016), Université Montesquieu - Bordeaux 4-Université Sciences et Technologies - Bordeaux 1-École Nationale Supérieure de Chimie et de Physique de Bordeaux (ENSCPB)-Institut de Chimie du CNRS (INC)-Centre National de la Recherche Scientifique (CNRS)-Université Montesquieu - Bordeaux 4-Université Sciences et Technologies - Bordeaux 1-École Nationale Supérieure de Chimie et de Physique de Bordeaux (ENSCPB)-Institut de Chimie du CNRS (INC)-Centre National de la Recherche Scientifique (CNRS)-Centre de Recherche sur l'Intégration Economique et Financière (CRIEF), Université de Poitiers-Université de Poitiers-LIttoral ENvironnement et Sociétés - UMRi 7266 (LIENSs), Université de La Rochelle (ULR)-Centre National de la Recherche Scientifique (CNRS)-Université de La Rochelle (ULR)-Centre National de la Recherche Scientifique (CNRS)-Institut de Chimie des Milieux et Matériaux de Poitiers (IC2MP), Centre National de la Recherche Scientifique (CNRS)-Institut de Chimie du CNRS (INC)-Université de Rennes 1 (UR1), Université de Rennes (UNIV-RENNES)-Université de Rennes (UNIV-RENNES)-Ecole Nationale Supérieure de Chimie de Rennes (ENSCR)-Institut National des Sciences Appliquées - Rennes (INSA Rennes), Institut National des Sciences Appliquées (INSA)-Université de Rennes (UNIV-RENNES)-Institut National des Sciences Appliquées (INSA)-Centre National de la Recherche Scientifique (CNRS)-Université de Rennes 1 (UR1), Institut National des Sciences Appliquées (INSA)-Université de Rennes (UNIV-RENNES)-Institut National des Sciences Appliquées (INSA)-Laboratoire de Chimie des Polymères Organiques (LCPO), Centre National de la Recherche Scientifique (CNRS)-Institut Polytechnique de Bordeaux-Ecole Nationale Supérieure de Chimie, de Biologie et de Physique (ENSCBP)-Université de Bordeaux (UB)-Institut de Chimie du CNRS (INC)-Centre National de la Recherche Scientifique (CNRS)-Institut Polytechnique de Bordeaux-Ecole Nationale Supérieure de Chimie, de Biologie et de Physique (ENSCBP)-Université de Bordeaux (UB)-Laboratoire de Génie Chimique (LGC), Université Fédérale Toulouse Midi-Pyrénées-Université Fédérale Toulouse Midi-Pyrénées-Centre National de la Recherche Scientifique (CNRS)-Institut National Polytechnique (Toulouse) (Toulouse INP), Université Fédérale Toulouse Midi-Pyrénées-Université Toulouse III - Paul Sabatier (UT3), Université Fédérale Toulouse Midi-Pyrénées-Unité de recherche sur les Biopolymères, Interactions Assemblages (BIA), and Institut National de Recherche pour l’Agriculture, l’Alimentation et l’Environnement (INRAE)-Institut National de Recherche pour l’Agriculture, l’Alimentation et l’Environnement (INRAE)
Subjects: Radical, Inorganic chemistry, Oxide, 010402 general chemistry, DFT, 01 natural sciences, 7. Clean energy, Biochemistry, Catalysis, Sonochemistry, Metal, chemistry.chemical_compound, Colloid and Surface Chemistry, Oxidation, Copper oxide, glucuronic acid, ultrasound, [CHIM.CATA]Chemical Sciences/Catalysis, General Chemistry, Glucuronic acid, 0104 chemical sciences, chemistry, visual_art, Gluconic acid, visual_art.visual_art_medium, Selectivity
Abstract: We report here, and rationalize, a synergistic effect between a non-noble metal oxide catalyst (CuO) and high-frequency ultrasound (HFUS) on glucose oxidation. While CuO and HFUS are able to independently oxidize glucose to gluconic acid, the combination of CuO with HFUS led to a dramatic change of the reaction selectivity, with glucuronic acid being formed as the major product. By means of density functional theory (DFT) calculations, we show that, under ultrasonic irradiation of water at 550 kHz, the surface lattice oxygen of a CuO catalyst traps H· radicals stemming from the sonolysis of water, making the ring-opening of glucose energetically unfavorable and leaving a high coverage of ·OH radical on the CuO surface, which selectively oxidizes glucose to glucuronic acid. This work also points toward a path to optimize the size of the catalyst particle for an ultrasonic frequency that minimizes the damage to the catalyst, resulting in its successful reuse.
Published: 2019

11. Charge Transfer Band Gap as an Indicator of Hysteresis in Li-Disordered Rock Salt Cathodes for Li-Ion Batteries

Author: Antonella Iadecola, Matthieu Saubanère, Marie-Liesse Doublet, Jean-Marie Tarascon, Jordi Cabana, Haifeng Li, Quentin Jacquet, Gwenaëlle Rousse, Erik J. Berg, Réseau sur le stockage électrochimique de l'énergie (RS2E), Université de Picardie Jules Verne (UPJV)-Institut de Chimie du CNRS (INC)-Aix Marseille Université (AMU)-Université de Pau et des Pays de l'Adour (UPPA)-Université de Nantes (UN)-Université de Montpellier (UM)-Centre National de la Recherche Scientifique (CNRS)-Sorbonne Université (SU)-Ecole Nationale Supérieure de Chimie de Paris - Chimie ParisTech-PSL (ENSCP), Université Paris sciences et lettres (PSL)-Université Paris sciences et lettres (PSL)-Université de Haute-Alsace (UHA) Mulhouse - Colmar (Université de Haute-Alsace (UHA))-Collège de France (CdF (institution))-Institut polytechnique de Grenoble - Grenoble Institute of Technology (Grenoble INP ), Université Grenoble Alpes (UGA)-Université Grenoble Alpes (UGA)-Institut National Polytechnique (Toulouse) (Toulouse INP), Université Fédérale Toulouse Midi-Pyrénées-Université Fédérale Toulouse Midi-Pyrénées-Ecole Nationale Supérieure de Chimie de Montpellier (ENSCM), Chaire Chimie du solide et énergie, Chimie du solide et de l'énergie (CSE), Collège de France (CdF (institution))-Institut de Chimie du CNRS (INC)-Sorbonne Université (SU)-Centre National de la Recherche Scientifique (CNRS)-Collège de France (CdF (institution))-Institut de Chimie du CNRS (INC)-Sorbonne Université (SU)-Centre National de la Recherche Scientifique (CNRS), Synchrotron SOLEIL (SSOLEIL), Centre National de la Recherche Scientifique (CNRS), Institut Charles Gerhardt Montpellier - Institut de Chimie Moléculaire et des Matériaux de Montpellier (ICGM ICMMM), Ecole Nationale Supérieure de Chimie de Montpellier (ENSCM)-Centre National de la Recherche Scientifique (CNRS)-Université de Montpellier (UM)-Université Montpellier 1 (UM1)-Université Montpellier 2 - Sciences et Techniques (UM2)-Institut de Chimie du CNRS (INC), University of Illinois [Chicago] (UIC), University of Illinois System, Paul Scherrer Institute (PSI), Université de Nantes (UN)-Aix Marseille Université (AMU)-Université de Haute-Alsace (UHA) Mulhouse - Colmar (Université de Haute-Alsace (UHA))-Collège de France (CdF (institution))-Université de Picardie Jules Verne (UPJV)-Ecole Nationale Supérieure de Chimie de Montpellier (ENSCM)-Ecole Nationale Supérieure de Chimie de Paris - Chimie ParisTech-PSL (ENSCP), Université Paris sciences et lettres (PSL)-Université Paris sciences et lettres (PSL)-Université de Pau et des Pays de l'Adour (UPPA)-Institut de Chimie du CNRS (INC)-Université de Montpellier (UM)-Sorbonne Université (SU)-Centre National de la Recherche Scientifique (CNRS)-Institut National Polytechnique (Toulouse) (Toulouse INP), Université de Toulouse (UT)-Université de Toulouse (UT)-Institut polytechnique de Grenoble - Grenoble Institute of Technology (Grenoble INP ), Université Grenoble Alpes (UGA)-Université Grenoble Alpes (UGA), Collège de France - Chaire Chimie du solide et énergie, Institut Charles Gerhardt Montpellier - Institut de Chimie Moléculaire et des Matériaux de Montpellier (ICGM), and Ecole Nationale Supérieure de Chimie de Montpellier (ENSCM)-Institut de Chimie du CNRS (INC)-Université de Montpellier (UM)-Centre National de la Recherche Scientifique (CNRS)
Subjects: chemistry.chemical_classification, Band gap, Chemistry, Cationic polymerization, Salt (chemistry), Charge (physics), General Chemistry, 010402 general chemistry, 01 natural sciences, Biochemistry, Redox, Catalysis, Cathode, 0104 chemical sciences, law.invention, Ion, Hysteresis, Colloid and Surface Chemistry, law, Chemical physics, [PHYS.COND.CM-MS]Physics [physics]/Condensed Matter [cond-mat]/Materials Science [cond-mat.mtrl-sci], ComputingMilieux_MISCELLANEOUS
Abstract: Disordered rock salt cathodes showing both anionic and cationic redox are being extensively studied for their very high energy storage capacity. Mn-based disordered rock salt compounds show much higher energy efficiency compared to the Ni-based materials as a result of the different voltage hysteresis, 0.5 and 2 V, respectively. To understand the origin of this difference, we herein report the design of two model compounds, Li
Published: 2019

12. Dinitrogen Cleavage by a Heterometallic Cluster Featuring Multiple Uranium-Rhodium Bonds

Author: Laurent Maron, Xiaoqing Xin, Yue Zhao, Shuao Wang, Congqing Zhu, Iskander Douair, Nanjing University (NJU), Laboratoire de physique et chimie des nano-objets (LPCNO), Institut National des Sciences Appliquées - Toulouse (INSA Toulouse), Institut National des Sciences Appliquées (INSA)-Université de Toulouse (UT)-Institut National des Sciences Appliquées (INSA)-Université de Toulouse (UT)-Institut de Chimie de Toulouse (ICT), Institut de Recherche pour le Développement (IRD)-Université Toulouse III - Paul Sabatier (UT3), Université de Toulouse (UT)-Université de Toulouse (UT)-Institut de Chimie du CNRS (INC)-Centre National de la Recherche Scientifique (CNRS)-Institut National Polytechnique (Toulouse) (Toulouse INP), Université de Toulouse (UT)-Institut de Recherche pour le Développement (IRD)-Université Toulouse III - Paul Sabatier (UT3), Université de Toulouse (UT)-Institut de Chimie du CNRS (INC)-Centre National de la Recherche Scientifique (CNRS)-Institut National Polytechnique (Toulouse) (Toulouse INP), Université de Toulouse (UT)-Institut de Recherche sur les Systèmes Atomiques et Moléculaires Complexes (IRSAMC), Université Toulouse III - Paul Sabatier (UT3), and Université de Toulouse (UT)-Université de Toulouse (UT)-Centre National de la Recherche Scientifique (CNRS)-Centre National de la Recherche Scientifique (CNRS)
Subjects: Chemistry, chemistry.chemical_element, General Chemistry, Nitride, Uranium, 010402 general chemistry, Triple bond, 01 natural sciences, Biochemistry, Catalysis, 0104 chemical sciences, Rhodium, Metal, Colloid and Surface Chemistry, Transition metal, visual_art, Polymer chemistry, visual_art.visual_art_medium, Cluster (physics), [PHYS.PHYS.PHYS-CHEM-PH]Physics [physics]/Physics [physics]/Chemical Physics [physics.chem-ph]
Abstract: Reduction of dinitrogen (N2) is a major challenge for chemists. Cooperation of multiple metal centers to break the strong N2 triple bond has been identified as a crucial step in both the industrial and the natural ammonia syntheses. However, reports of the cleavage of N2 by a multimetallic uranium complex remain extremely rare, although uranium species were used as catalyst in the early Harber-Bosch process. Here we report the cleavage of N2 to two nitrides by a multimetallic uranium-rhodium cluster at ambient temperature and pressure. The nitride product further reacts with acid to give substantial yields of ammonium. The presence of uranium-rhodium bond in this multimetallic cluster was revealed by X-ray crystallographic and computational studies. This study demonstrates that the multimetallic clusters containing uranium and transition metals are promising materials for N2 fixation and reduction.
Published: 2020

13. Two-Electron Oxidative Atom Transfer at a Homoleptic, Tetravalent Uranium Complex

Author: John Bacsa, Natalie T. Rice, Karl McCabe, Laurent Maron, Henry S. La Pierre, Georgia Institute of Technology [Atlanta], Laboratoire de physique et chimie des nano-objets (LPCNO), Institut National des Sciences Appliquées - Toulouse (INSA Toulouse), Institut National des Sciences Appliquées (INSA)-Université de Toulouse (UT)-Institut National des Sciences Appliquées (INSA)-Université de Toulouse (UT)-Institut de Chimie de Toulouse (ICT), Institut de Recherche pour le Développement (IRD)-Université Toulouse III - Paul Sabatier (UT3), Université de Toulouse (UT)-Université de Toulouse (UT)-Institut de Chimie du CNRS (INC)-Centre National de la Recherche Scientifique (CNRS)-Institut National Polytechnique (Toulouse) (Toulouse INP), Université de Toulouse (UT)-Institut de Recherche pour le Développement (IRD)-Université Toulouse III - Paul Sabatier (UT3), Université de Toulouse (UT)-Institut de Chimie du CNRS (INC)-Centre National de la Recherche Scientifique (CNRS)-Institut National Polytechnique (Toulouse) (Toulouse INP), Université de Toulouse (UT)-Institut de Recherche sur les Systèmes Atomiques et Moléculaires Complexes (IRSAMC), Université Toulouse III - Paul Sabatier (UT3), and Université de Toulouse (UT)-Université de Toulouse (UT)-Centre National de la Recherche Scientifique (CNRS)-Centre National de la Recherche Scientifique (CNRS)
Subjects: Chemistry, chemistry.chemical_element, General Chemistry, Oxidative phosphorylation, Electron, Nitrous oxide, Uranium, 010402 general chemistry, 01 natural sciences, Biochemistry, Catalysis, 0104 chemical sciences, chemistry.chemical_compound, Crystallography, Colloid and Surface Chemistry, Atom, Azide, [PHYS.PHYS.PHYS-CHEM-PH]Physics [physics]/Physics [physics]/Chemical Physics [physics.chem-ph], Homoleptic
Abstract: A tetrahomoleptic, pseudotetrahedral U4+ imidophosphorane complex, [U(NP(pip)3)4], 1-U(PN), is reported. This complex can be oxidized by two electrons with either mesityl azide or nitrous oxide. Th...
Published: 2020

14. Electrolyte Reactivity in the Double Layer in Mg Batteries: An Interface Potential-Dependent DFT Study

Author: Jean-Sébastien Filhol, T. Rejec, Robert Dominko, Marie-Liesse Doublet, Jan Bitenc, Anja Kopač Lautar, Laboratory for Materials Electrochemistry, National Institute of Chemistry, Institut Charles Gerhardt Montpellier - Institut de Chimie Moléculaire et des Matériaux de Montpellier (ICGM ICMMM), Université Montpellier 1 (UM1)-Université Montpellier 2 - Sciences et Techniques (UM2)-Ecole Nationale Supérieure de Chimie de Montpellier (ENSCM)-Université de Montpellier (UM)-Centre National de la Recherche Scientifique (CNRS), University of Ljubljana, Jozef Stefan Institute [Ljubljana] (IJS), Advanced Lithium Energy Storage Systems - ALISTORE-ERI (ALISTORE-ERI), Institut de Chimie du CNRS (INC)-Centre National de la Recherche Scientifique (CNRS), Ecole Nationale Supérieure de Chimie de Montpellier (ENSCM)-Centre National de la Recherche Scientifique (CNRS)-Université de Montpellier (UM)-Université Montpellier 1 (UM1)-Université Montpellier 2 - Sciences et Techniques (UM2)-Institut de Chimie du CNRS (INC), Réseau sur le stockage électrochimique de l'énergie (RS2E), Université de Picardie Jules Verne (UPJV)-Institut de Chimie du CNRS (INC)-Aix Marseille Université (AMU)-Université de Pau et des Pays de l'Adour (UPPA)-Université de Nantes (UN)-Université de Montpellier (UM)-Centre National de la Recherche Scientifique (CNRS)-Sorbonne Université (SU)-Ecole Nationale Supérieure de Chimie de Paris - Chimie ParisTech-PSL (ENSCP), Université Paris sciences et lettres (PSL)-Université Paris sciences et lettres (PSL)-Université de Haute-Alsace (UHA) Mulhouse - Colmar (Université de Haute-Alsace (UHA))-Collège de France (CdF (institution))-Institut polytechnique de Grenoble - Grenoble Institute of Technology (Grenoble INP ), Université Grenoble Alpes (UGA)-Université Grenoble Alpes (UGA)-Institut National Polytechnique (Toulouse) (Toulouse INP), Université Fédérale Toulouse Midi-Pyrénées-Université Fédérale Toulouse Midi-Pyrénées-Ecole Nationale Supérieure de Chimie de Montpellier (ENSCM), Institut Charles Gerhardt Montpellier - Institut de Chimie Moléculaire et des Matériaux de Montpellier (ICGM), Ecole Nationale Supérieure de Chimie de Montpellier (ENSCM)-Institut de Chimie du CNRS (INC)-Université de Montpellier (UM)-Centre National de la Recherche Scientifique (CNRS), Université de Nantes (UN)-Aix Marseille Université (AMU)-Université de Haute-Alsace (UHA) Mulhouse - Colmar (Université de Haute-Alsace (UHA))-Collège de France (CdF (institution))-Université de Picardie Jules Verne (UPJV)-Ecole Nationale Supérieure de Chimie de Montpellier (ENSCM)-Ecole Nationale Supérieure de Chimie de Paris - Chimie ParisTech-PSL (ENSCP), Université Paris sciences et lettres (PSL)-Université Paris sciences et lettres (PSL)-Université de Pau et des Pays de l'Adour (UPPA)-Institut de Chimie du CNRS (INC)-Université de Montpellier (UM)-Sorbonne Université (SU)-Centre National de la Recherche Scientifique (CNRS)-Institut National Polytechnique (Toulouse) (Toulouse INP), Université de Toulouse (UT)-Université de Toulouse (UT)-Institut polytechnique de Grenoble - Grenoble Institute of Technology (Grenoble INP ), and Université Grenoble Alpes (UGA)-Université Grenoble Alpes (UGA)
Subjects: Double layer (biology), Battery (electricity), Chemical substance, General Chemistry, Electrolyte, 010402 general chemistry, Electrochemistry, 01 natural sciences, Biochemistry, Catalysis, Dimethoxyethane, 0104 chemical sciences, [CHIM.THEO]Chemical Sciences/Theoretical and/or physical chemistry, chemistry.chemical_compound, Colloid and Surface Chemistry, chemistry, Chemical engineering, [CHIM]Chemical Sciences, Chemical stability, [CHIM.OTHE]Chemical Sciences/Other, Ethylene carbonate, ComputingMilieux_MISCELLANEOUS
Abstract: International audience; The electrochemical degradation of two solvent-based electrolytes for Mg-metal batteries is investigated through a Grand canonical DFT approach. Both electrolytes are highly reactive in the double layer region where the solvated species have no direct contact with the Mg-surface, hence emphasising that surface reactions are not the only phenomena responsible for electrolyte degradation. Applied to dimethoxyethane (DME) and ethylene carbonate (EC), the present methodology shows that both solvents should thermodynamically decompose in the double layer prior to the Mg 2+ /Mg 0 reduction, leading to electrochemically inactive reaction products. Based on thermodynamic considerations, Mg 0 deposition should not be possible, which is not in agreement with experiments, at least for DME-based electrolytes. This apparent contradiction is here addressed through the rationalization of the electrochemical mechanism underlying solvent electro-activation. An extended operation potential window (OPW) is defined, in which the Mg 2+ /Mg 0 reduction can compete with electrolyte decomposition, thus enabling battery operation beyond the solvated species thermodynamic stability. The chemical study of the degradation products is in excellent agreement with experiments and it offer rationale for the Mg-battery failure in EC electrolyte and 2 capacity fade in DME electrolyte. Potential-dependent approach proposed herein is thus able to successfully tackle the challenging problem of interface electrochemistry. Being fully transferable to any other electrochemical systems, this methodology should provide rational guidelines for the development of viable electrolytes for multivalent batteries, and more generally, energy conversion and storage devices.
Published: 2020
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15. Ethene Activation and Catalytic Hydrogenation by a Low-Valent Uranium Pentalene Complex

Author: F. Geoffrey N. Cloke, Richard A. Layfield, Alexander F. R. Kilpatrick, Laurent Maron, Nikolaos Tsoureas, University of Sussex, Laboratoire de physique et chimie des nano-objets (LPCNO), Institut National des Sciences Appliquées - Toulouse (INSA Toulouse), Institut National des Sciences Appliquées (INSA)-Université de Toulouse (UT)-Institut National des Sciences Appliquées (INSA)-Université de Toulouse (UT)-Institut de Chimie de Toulouse (ICT), Institut de Recherche pour le Développement (IRD)-Université Toulouse III - Paul Sabatier (UT3), Université de Toulouse (UT)-Université de Toulouse (UT)-Institut de Chimie du CNRS (INC)-Centre National de la Recherche Scientifique (CNRS)-Institut National Polytechnique (Toulouse) (Toulouse INP), Université de Toulouse (UT)-Institut de Recherche pour le Développement (IRD)-Université Toulouse III - Paul Sabatier (UT3), Université de Toulouse (UT)-Institut de Chimie du CNRS (INC)-Centre National de la Recherche Scientifique (CNRS)-Institut National Polytechnique (Toulouse) (Toulouse INP), Université de Toulouse (UT)-Institut de Recherche sur les Systèmes Atomiques et Moléculaires Complexes (IRSAMC), Université Toulouse III - Paul Sabatier (UT3), Université de Toulouse (UT)-Université de Toulouse (UT)-Centre National de la Recherche Scientifique (CNRS)-Centre National de la Recherche Scientifique (CNRS), and Humboldt University Of Berlin
Subjects: Pentalene, Hydrogen, Atmospheric pressure, Chemistry, Orbital hybridisation, chemistry.chemical_element, General Chemistry, Uranium, Biochemistry, Medicinal chemistry, Bond order, Catalysis, chemistry.chemical_compound, Colloid and Surface Chemistry, Oxidation state, Single bond, [PHYS.PHYS.PHYS-CHEM-PH]Physics [physics]/Physics [physics]/Chemical Physics [physics.chem-ph], QD0146
Abstract: The reaction of the uranium(III) complex [U(η8-Pn††)(η5-Cp*)] (1) (Pn†† = C8H4(1,4-SiiPr3)2, Cp* = C5Me5) with ethene at atmospheric pressure produces the ethene-bridged diuranium complex [{(η8-Pn††)(η5-Cp*)U}2(μ-η2:η2-C2H4)] (2). A computational analysis of 2 revealed that coordination of ethene to uranium reduces the carbon–carbon bond order from 2 to a value consistent with a single bond, with a concomitant change in the formal uranium oxidation state from +3 in 1 to +4 in 2. Furthermore, the uranium–ethene bonding in 2 is of the δ type, with the dominant uranium contribution being from f–d hybrid orbitals. Complex 2 reacts with hydrogen to produce ethane and reform 1, leading to the discovery that complex 1 also catalyzes the hydrogenation of ethene under ambient conditions.
Published: 2019

16. When Light and Acid Play Tic-Tac-Toe with a Nine-State Molecular Switch

Author: Stéphanie Delbaere, Lionel Sanguinet, Stéphane Aloïse, Philippe Leriche, Clément Guerrin, Youssef Aidibi, Maylis Orio, Laboratoire de chimie de coordination (LCC), Institut de Chimie de Toulouse (ICT), Institut de Recherche pour le Développement (IRD)-Université Toulouse III - Paul Sabatier (UT3), Université de Toulouse (UT)-Université de Toulouse (UT)-Institut de Chimie du CNRS (INC)-Centre National de la Recherche Scientifique (CNRS)-Institut National Polytechnique (Toulouse) (Toulouse INP), Université de Toulouse (UT)-Institut de Recherche pour le Développement (IRD)-Université Toulouse III - Paul Sabatier (UT3), Université de Toulouse (UT)-Centre National de la Recherche Scientifique (CNRS), MOLTECH-Anjou, Université d'Angers (UA)-Institut de Chimie du CNRS (INC)-Centre National de la Recherche Scientifique (CNRS), Chimie, Ingénierie Moléculaire et Matériaux d'Angers (CIMMA), Université d'Angers (UA)-Centre National de la Recherche Scientifique (CNRS), Laboratoire Avancé de Spectroscopie pour les Intéractions la Réactivité et l'Environnement - UMR 8516 (LASIRE), Institut de Chimie du CNRS (INC)-Université de Lille-Centre National de la Recherche Scientifique (CNRS), Institut des Sciences Moléculaires de Marseille (ISM2), Aix Marseille Université (AMU)-École Centrale de Marseille (ECM)-Institut de Chimie du CNRS (INC)-Centre National de la Recherche Scientifique (CNRS), Institut National Polytechnique (Toulouse) (Toulouse INP), Université Fédérale Toulouse Midi-Pyrénées-Université Fédérale Toulouse Midi-Pyrénées-Université Toulouse III - Paul Sabatier (UT3), Université Fédérale Toulouse Midi-Pyrénées-Institut de Chimie de Toulouse (ICT-FR 2599), Université Fédérale Toulouse Midi-Pyrénées-Université Fédérale Toulouse Midi-Pyrénées-Centre National de la Recherche Scientifique (CNRS)-Institut de Recherche pour le Développement (IRD)-Université Toulouse III - Paul Sabatier (UT3), Université Fédérale Toulouse Midi-Pyrénées-Institut de Chimie du CNRS (INC)-Centre National de la Recherche Scientifique (CNRS)-Institut de Recherche pour le Développement (IRD)-Institut de Chimie du CNRS (INC)-Centre National de la Recherche Scientifique (CNRS), and Institut de Chimie du CNRS (INC)-Université de Lille-Centre National de la Recherche Scientifique (CNRS)-Centrale Lille Institut (CLIL)
Subjects: Molecular switch, Oxazolidine, Kinetics, General Chemistry, State (functional analysis), 010402 general chemistry, Ring (chemistry), 01 natural sciences, Biochemistry, Catalysis, 0104 chemical sciences, Crystallography, chemistry.chemical_compound, Colloid and Surface Chemistry, chemistry, [CHIM.ANAL]Chemical Sciences/Analytical chemistry, [CHIM]Chemical Sciences, Molecule, Commutation, Isomerization
Abstract: International audience; Combining different molecular switching functions in a single molecule is a simple strategy to develop commutable molecules featuring more than two commutation states. The present study reports on two molecular systems consisting of two indolino-oxazolidine (Box) moieties connected to an aromatic bridge (phenyl or bithiophene) by ethylenic junctions. Such systems, referenced as BiBox, are expected to show up multiaddressable and multiresponsive behaviors. On one hand, the oxazolidine ring opening/closure of Box moieties can be addressed by chemical stimuli, and on the other hand, the trans-to-cis isomerization of the ethylenic junctions is induced by visible light irradiation (with a thermal back conversion). NMR and UV−visible spectroscopies allowed to characterize up to nine out of the ten theoretically expected commutation states as well as to measure the kinetics of the interconversions. Also, steady state fluorescence spectroscopy measurements highlighted the strong influence of the open/closed states of the Box moieties on their emission properties.
Published: 2019

17. Divalent Ytterbium Complex-Catalyzed Homo- and Cross-Coupling of Primary Arylsilanes

Author: Li Xiang, Xiaojuan Liu, Laurent Maron, Yaofeng Chen, Elisa Louyriac, Xuebing Leng, Shanghai Institute of Materia Medica - Chinese Academy of Sciences [Shanghai], Shanghai Institute of Organic Chemistry - Chinese Academy of Sciences, Laboratoire de physique et chimie des nano-objets (LPCNO), Institut National des Sciences Appliquées - Toulouse (INSA Toulouse), Institut National des Sciences Appliquées (INSA)-Université de Toulouse (UT)-Institut National des Sciences Appliquées (INSA)-Université de Toulouse (UT)-Institut de Chimie de Toulouse (ICT), Institut de Recherche pour le Développement (IRD)-Université Toulouse III - Paul Sabatier (UT3), Université de Toulouse (UT)-Université de Toulouse (UT)-Institut de Chimie du CNRS (INC)-Centre National de la Recherche Scientifique (CNRS)-Institut National Polytechnique (Toulouse) (Toulouse INP), Université de Toulouse (UT)-Institut de Recherche pour le Développement (IRD)-Université Toulouse III - Paul Sabatier (UT3), Université de Toulouse (UT)-Institut de Chimie du CNRS (INC)-Centre National de la Recherche Scientifique (CNRS)-Institut National Polytechnique (Toulouse) (Toulouse INP), Université de Toulouse (UT)-Institut de Recherche sur les Systèmes Atomiques et Moléculaires Complexes (IRSAMC), Université Toulouse III - Paul Sabatier (UT3), Université de Toulouse (UT)-Université de Toulouse (UT)-Centre National de la Recherche Scientifique (CNRS)-Centre National de la Recherche Scientifique (CNRS), University of Chinese Academy of Sciences [Beijing] (UCAS), National Natural Science Foundation of China [21602237, 21732007, 21890721, 21821002], Program of Shanghai Academic Research Leader, Strategic Priority Research Program of the Chinese Academy of Sciences [XDB20000000], Fujian Institute of Innovation, Chinese Academy of Sciences, and Chinese Academy of Sciences President's International Fellowship Initiative
Subjects: chemistry.chemical_classification, Silanes, Chemistry, Hypervalent molecule, General Chemistry, 010402 general chemistry, 01 natural sciences, Biochemistry, Catalysis, 0104 chemical sciences, Divalent, chemistry.chemical_compound, Colloid and Surface Chemistry, Polymer chemistry, Redistribution (chemistry), [PHYS.PHYS.PHYS-CHEM-PH]Physics [physics]/Physics [physics]/Chemical Physics [physics.chem-ph], Selectivity, Bond cleavage, Alkyl
Abstract: International audience; Redistribution of primary silanes through C-Si and Si-H bond cleavage and reformation provides a straightforward synthesis of secondary silanes, but the poor selectivity and low efficiency severely hinders the application of this synthetic protocol. Here, we show that a newly synthesized divalent ytterbium alkyl complex exhibits unprecedentedly high catalytic activity toward the selective redistribution of primary arylsilanes to secondary arylsilanes. More significantly, this complex also effectively catalyzes the cross-coupling between electron-withdrawing substituted primary arylsilanes and electron-donating substituted primary arylsilanes to secondary arylsilanes containing two different aryls. DFT calculation indicates that the reaction always involve the exothermic formation of a hypervalent silicon upon facile addition of PhSiH3 to the Yb-E (E = C, H) bond. This hypervalent compound can easily either generate directly the Yb-Ph complex, or indirectly through the formation of Yb-H, that is the key complex for the formation of Ph2SiH2.
Published: 2018

18. Heterotetrametallic Re-Zn-Zn-Re Complex Generated by an Anionic Rhenium(I) β-Diketiminate

Author: Robert G. Bergman, Laurent Maron, John Arnold, Trevor D. Lohrey, Department of Chemistry [Berkeley], University of California [Berkeley] (UC Berkeley), University of California (UC)-University of California (UC), Laboratoire de physique et chimie des nano-objets (LPCNO), Institut National des Sciences Appliquées - Toulouse (INSA Toulouse), Institut National des Sciences Appliquées (INSA)-Université de Toulouse (UT)-Institut National des Sciences Appliquées (INSA)-Université de Toulouse (UT)-Institut de Chimie de Toulouse (ICT), Institut de Recherche pour le Développement (IRD)-Université Toulouse III - Paul Sabatier (UT3), Université de Toulouse (UT)-Université de Toulouse (UT)-Institut de Chimie du CNRS (INC)-Centre National de la Recherche Scientifique (CNRS)-Institut National Polytechnique (Toulouse) (Toulouse INP), Université de Toulouse (UT)-Institut de Recherche pour le Développement (IRD)-Université Toulouse III - Paul Sabatier (UT3), Université de Toulouse (UT)-Institut de Chimie du CNRS (INC)-Centre National de la Recherche Scientifique (CNRS)-Institut National Polytechnique (Toulouse) (Toulouse INP), Université de Toulouse (UT)-Institut de Recherche sur les Systèmes Atomiques et Moléculaires Complexes (IRSAMC), Université Toulouse III - Paul Sabatier (UT3), Université de Toulouse (UT)-Université de Toulouse (UT)-Centre National de la Recherche Scientifique (CNRS)-Centre National de la Recherche Scientifique (CNRS), NSF [CHE1465188], U.S. DOE Integrated University Program, Chinese Academy of Science, Humboldt Foundation, and Office of Science, Office of Basic Energy Sciences, of the U.S. DOE [DE-AC02-05CH11231]
Subjects: Hydride, chemistry.chemical_element, Protonation, General Chemistry, Zinc, Rhenium, 010402 general chemistry, 01 natural sciences, Biochemistry, Catalysis, 0104 chemical sciences, β diketiminate, Colloid and Surface Chemistry, chemistry, Covalent bond, Polymer chemistry, [PHYS.PHYS.PHYS-CHEM-PH]Physics [physics]/Physics [physics]/Chemical Physics [physics.chem-ph], Trifluoromethanesulfonate
Abstract: International audience; We report the synthesis of an anionic rhenium(I) compound, Na[Re(eta(5)-Cp)(BDI)] (1; Cp = cyclopentadienide, BDI = N,N'-bis(2,6-diisopropylphenyl)-3,5-dimethyl-beta-diketiminate) and initial investigations of its use as a strong chemical reductant and metalloligand. Chemical oxidation of 1 gives a rare example of a rhenium(II) compound Re(eta(5)-Cp)(BDI) (2), while protonation of 1 yields the rhenium(III) hydride complex Re(H)(eta(5)-Cp)(BDI) (3). The reaction of 1 with ZnCl2 generated both 2 and the zinc(I) compound [ZnRe(eta(5)-Cp)(BDI)](2) (4), which features a linear, tetrametallic Re(I)-Zn(I)-Zn(I)-Re(I) core. Computational studies of 4 were performed to characterize the metal-metal bonding interactions; the results indicate a dative interaction from rhenium to zinc and covalent bonding between the two zinc centers. One-electron oxidation of 4 yielded both 2 and the triflate-bridged zinc(II) complex [(mu-OTOZnRe(eta(5)-Cp)(BDI)](2) (5, OTf = trifluoromethanesulfonate).
Published: 2018

19. The Nature of Secondary Interactions at Electrophilic Metal Sites of Molecular and Silica-Supported Organolutetium Complexes from Solid-State NMR Spectroscopy

Author: Richard A. Andersen, Laurent Maron, Christophe Copéret, Anne Lesage, Wayne W. Lukens, Kevin J. Sanders, David Gajan, Iker del Rosal, Matthew P. Conley, Giuseppe Lapadula, Department of Chemistry and Applied Biosciences [ETH Zürich], Eidgenössische Technische Hochschule - Swiss Federal Institute of Technology [Zürich] (ETH Zürich), Biological Solid-State NMR Methods - Méthodes de RMN à l'état solide en biologie, Institut des Sciences Analytiques (ISA), Institut de Chimie du CNRS (INC)-Université Claude Bernard Lyon 1 (UCBL), Université de Lyon-Université de Lyon-Centre National de la Recherche Scientifique (CNRS)-Institut de Chimie du CNRS (INC)-Université Claude Bernard Lyon 1 (UCBL), Université de Lyon-Université de Lyon-Centre National de la Recherche Scientifique (CNRS), Solid-State NMR Methods for Materials - Méthodes de RMN à l'état solide pour les matériaux, Laboratoire de physique et chimie des nano-objets (LPCNO), Institut National des Sciences Appliquées - Toulouse (INSA Toulouse), Institut National des Sciences Appliquées (INSA)-Institut National des Sciences Appliquées (INSA)-Institut de Chimie de Toulouse (ICT-FR 2599), Institut National Polytechnique (Toulouse) (Toulouse INP), Université Fédérale Toulouse Midi-Pyrénées-Université Fédérale Toulouse Midi-Pyrénées-Centre National de la Recherche Scientifique (CNRS)-Institut de Recherche pour le Développement (IRD)-Université Toulouse III - Paul Sabatier (UT3), Université Fédérale Toulouse Midi-Pyrénées-Institut de Chimie du CNRS (INC)-Institut National Polytechnique (Toulouse) (Toulouse INP), Université Fédérale Toulouse Midi-Pyrénées-Institut de Chimie du CNRS (INC)-Institut de Recherche sur les Systèmes Atomiques et Moléculaires Complexes (IRSAMC), Institut National des Sciences Appliquées (INSA)-Institut National des Sciences Appliquées (INSA)-Université Toulouse III - Paul Sabatier (UT3), Université Fédérale Toulouse Midi-Pyrénées-Université Fédérale Toulouse Midi-Pyrénées-Centre National de la Recherche Scientifique (CNRS)-Centre National de la Recherche Scientifique (CNRS), Lawrence Berkeley National Laboratory [Berkeley] (LBNL), Department of Chemistry [Berkeley], University of California [Berkeley], University of California-University of California, C.C. thanks the Miller Institute for a Visiting Professor position at UC Berkeley, during which this manuscript was finalized. Portions of this work were performed at Lawrence Berkeley National Laboratory under contract no. DE-AC02-05CH11231 and at the Stanford Synchrotron Radiation Lightsource (SSRL). Use of the Stanford Synchrotron Radiation Lightsource, SLAC National Accelerator Laboratory, is supported by the U.S. Department of Energy, Office of Science, Office of Basic Energy Sciences under contract no. DE-AC02-76SF00515. Portions of this work were supported by the U.S. Department of Energy, Office of Science, Basic Energy Sciences, Chemical Sciences, Biosciences, and Geosciences Division (CSGB), Heavy Element Chemistry Program and were performed at Lawrence Berkeley National Laboratory under contract no. DE-AC02-05CH11231. We also thank the HPCs CALcul en Midi-Pyrennes (CALIMP-EOS, grant P0833) for the generous allocation of computer time. Financial support from the TGIR-RMN-THC Fr3050 CNRS for conducting the research is gratefully acknowledged., Université Claude Bernard Lyon 1 (UCBL), Université de Lyon-Université de Lyon-Institut de Chimie du CNRS (INC)-Centre National de la Recherche Scientifique (CNRS)-Université Claude Bernard Lyon 1 (UCBL), Université de Lyon-Université de Lyon-Institut de Chimie du CNRS (INC)-Centre National de la Recherche Scientifique (CNRS), Institut National des Sciences Appliquées (INSA)-Université de Toulouse (UT)-Institut National des Sciences Appliquées (INSA)-Université de Toulouse (UT)-Institut de Chimie de Toulouse (ICT), Institut de Recherche pour le Développement (IRD)-Université Toulouse III - Paul Sabatier (UT3), Université de Toulouse (UT)-Université de Toulouse (UT)-Institut de Chimie du CNRS (INC)-Centre National de la Recherche Scientifique (CNRS)-Institut National Polytechnique (Toulouse) (Toulouse INP), Université de Toulouse (UT)-Institut de Recherche pour le Développement (IRD)-Université Toulouse III - Paul Sabatier (UT3), Université de Toulouse (UT)-Institut de Chimie du CNRS (INC)-Centre National de la Recherche Scientifique (CNRS)-Institut National Polytechnique (Toulouse) (Toulouse INP), Université de Toulouse (UT)-Institut de Recherche sur les Systèmes Atomiques et Moléculaires Complexes (IRSAMC), Université Toulouse III - Paul Sabatier (UT3), Université de Toulouse (UT)-Université de Toulouse (UT)-Centre National de la Recherche Scientifique (CNRS)-Centre National de la Recherche Scientifique (CNRS), University of California [Berkeley] (UC Berkeley), and University of California (UC)-University of California (UC)
Subjects: 010405 organic chemistry, Chemistry, Resonance, Nanotechnology, General Chemistry, Nuclear magnetic resonance spectroscopy, 010402 general chemistry, 01 natural sciences, Biochemistry, Catalysis, Spectral line, 0104 chemical sciences, Crystallography, Colloid and Surface Chemistry, Solid-state nuclear magnetic resonance, [CHIM.ANAL]Chemical Sciences/Analytical chemistry, Chemical Sciences, Electrophile, Proton NMR, [CHIM]Chemical Sciences, Spectroscopy, Natural bond orbital
Abstract: International audience; Lu[CH(SiMe3)2]3 reacts with [SiO2-700] to give [(≡SiO)Lu[CH(SiMe3)2]2] and CH2(SiMe3)2. [(≡SiO)Lu[CH(SiMe3)2]2] is characterized by solid-state NMR and EXAFS spectroscopy, which show that secondary Lu···C and Lu···O interactions, involving a γ-CH3 and a siloxane bridge, are present. From X-ray crystallographic analysis, the molecular analogues Lu[CH(SiMe3)2]3-x[O-2,6-tBu-C6H3]x (x = 0-2) also have secondary Lu···C interactions. The (1)H NMR spectrum of Lu[CH(SiMe3)2]3 shows that the -SiMe3 groups are equivalent to -125 °C and inequivalent below that temperature, ΔG(⧧)(Tc = 148 K) = 7.1 kcal mol(-1). Both -SiMe3 groups in Lu[CH(SiMe3)2]3 have (1)JCH = 117 ± 1 Hz at -140 °C. The solid-state (13)C CPMAS NMR spectrum at 20 °C shows three chemically inequivalent resonances in the area ratio of 4:1:1 (12:3:3); the J-resolved spectra for each resonance give (1)JCH = 117 ± 2 Hz. The (29)Si CPMAS NMR spectrum shows two chemically inequivalent resonances with different values of chemical shift anisotropy. Similar observations are obtained for Lu[CH(SiMe3)2]3-x[O-2,6-tBu-C6H3]x (x = 1 and 2). The spectroscopic data point to short Lu···Cγ contacts corresponding to 3c-2e Lu···Cγ-Siβ interactions, which are supported by DFT calculations. Calculated natural bond orbital (NBO) charges show that Cγ carries a negative charge, while Lu, Hγ, and Siβ carry positive charges; as the number of O-based ligands increases so does the positive charge at Lu, which in turns shortens the Lu···Cγ distance. The change in NBO charges and the resulting changes in the spectroscopic and crystallographic properties show how ligands and surface-support sites rearrange to accommodate these changes, consistent with Pauling's electroneutrality concept.
Published: 2016

20. Experimental and Theoretical Studies on the Implications of Halide-Dependent Aqueous Solvation of Sm(II)

Author: Laurent Maron, Jorge Hernández-Cobos, Anna M. Li, William R. Anderson, Robert A. Flowers, Alejandro Ramírez-Solís, Caroline O. Bartulovich, Tesia V. Chciuk, Humberto Saint-Martin, Universidad Autonoma del Estado de Morelos (UAEM), Lehigh University [Bethlehem], Universidad Nacional Autónoma de México = National Autonomous University of Mexico (UNAM), Laboratoire de physique et chimie des nano-objets (LPCNO), Institut National des Sciences Appliquées - Toulouse (INSA Toulouse), Institut National des Sciences Appliquées (INSA)-Université de Toulouse (UT)-Institut National des Sciences Appliquées (INSA)-Université de Toulouse (UT)-Institut de Chimie de Toulouse (ICT), Institut de Recherche pour le Développement (IRD)-Université Toulouse III - Paul Sabatier (UT3), Université de Toulouse (UT)-Université de Toulouse (UT)-Institut de Chimie du CNRS (INC)-Centre National de la Recherche Scientifique (CNRS)-Institut National Polytechnique (Toulouse) (Toulouse INP), Université de Toulouse (UT)-Institut de Recherche pour le Développement (IRD)-Université Toulouse III - Paul Sabatier (UT3), Université de Toulouse (UT)-Institut de Chimie du CNRS (INC)-Centre National de la Recherche Scientifique (CNRS)-Institut National Polytechnique (Toulouse) (Toulouse INP), Université de Toulouse (UT)-Institut de Recherche sur les Systèmes Atomiques et Moléculaires Complexes (IRSAMC), Université Toulouse III - Paul Sabatier (UT3), Université de Toulouse (UT)-Université de Toulouse (UT)-Centre National de la Recherche Scientifique (CNRS)-Centre National de la Recherche Scientifique (CNRS), National Science Foundation [CHE1565741], CONACYT Basic Science [253679], and DGAPA-UNAM [IN101599, IG100416]
Subjects: Aqueous solution, 010405 organic chemistry, Chemistry, Inorganic chemistry, Solvation, Halide, chemistry.chemical_element, General Chemistry, 010402 general chemistry, 01 natural sciences, Biochemistry, Catalysis, 0104 chemical sciences, Samarium, Reduction (complexity), Colloid and Surface Chemistry, [PHYS.PHYS.PHYS-CHEM-PH]Physics [physics]/Physics [physics]/Chemical Physics [physics.chem-ph]
Abstract: International audience; The addition of water to samarium(II) has been demonstrated to have a significant impact on the reduction of organic substrates, with the majority of research dedicated to the most widely used reagent, samarium diiodide (SmI2). The work presented herein focuses on the reducing capabilities of samarium dibromide (SmBr2) and demonstrates how the modest change in halide ligand results in observable mechanistic differences between the SmBr2-water and the SmI2-water systems that have considerable implications in terms of reactivity between the two reagents. Quantum chemical results from Born-Oppenheimer molecular dynamics simulations show significant differences between SmI2-water and SmBr2-water, with the latter displaying less dissociation of the halide, which results in a lower coordination number for water. Experimental results are consistent with computational results and demonstrate that the coordination sphere of SmBr2 is saturated at lower concentrations of water. In addition, coordination-induced bond-weakening of the O-H bond is demonstrably different for water bound to SmBr2, leading to an estimated O-H bond-weakening of at least 83 kcal/mol, nearly 10 kcal/mol larger than the bond-weakening observed in SmI2-H2O. Experimental results also demonstrate that the use of alcohols in place of water with SmBr2 leads to substrate reduction, albeit several orders of magnitude slower than for SmBr2-water. The difference in rates resulting from the change in proton donor is attributed to a rate-limiting proton-coupled electron transfer in SmBr2-water and a sequential electron transfer then proton transfer in SmBr2-alcohol systems, where electron transfer is rate-limiting.
Published: 2018

21. Complete Set of Elastic Moduli of a Spin-Crossover Solid: Spin-State Dependence and Mechanical Actuation

Author: Azzedine Bousseksou, Ines E. Collings, Mirko Mikolasek, Victoria Shalabaeva, Gábor Molnár, Thierry Leichle, Karl Ridier, Sylvain Rat, Alin-Ciprian Bas, William Nicolazzi, Jean Cacheux, Liviu Nicu, Maria Dolores Manrique-Juarez, Helena J. Shepherd, Lionel Salmon, Fabrice Mathieu, European Synchrotron Radiation Facility (ESRF), Laboratoire de chimie de coordination (LCC), Institut National Polytechnique (Toulouse) (Toulouse INP), Université Fédérale Toulouse Midi-Pyrénées-Université Fédérale Toulouse Midi-Pyrénées-Université Toulouse III - Paul Sabatier (UT3), Université Fédérale Toulouse Midi-Pyrénées-Institut de Chimie de Toulouse (ICT-FR 2599), Université Fédérale Toulouse Midi-Pyrénées-Université Fédérale Toulouse Midi-Pyrénées-Centre National de la Recherche Scientifique (CNRS)-Institut de Recherche pour le Développement (IRD)-Université Toulouse III - Paul Sabatier (UT3), Université Fédérale Toulouse Midi-Pyrénées-Institut de Chimie du CNRS (INC)-Centre National de la Recherche Scientifique (CNRS)-Institut de Recherche pour le Développement (IRD)-Institut de Chimie du CNRS (INC)-Centre National de la Recherche Scientifique (CNRS), Université Toulouse III - Paul Sabatier (UT3), Université Fédérale Toulouse Midi-Pyrénées, Laboratoire d'analyse et d'architecture des systèmes (LAAS), Université Toulouse - Jean Jaurès (UT2J)-Université Toulouse 1 Capitole (UT1), Université Fédérale Toulouse Midi-Pyrénées-Université Fédérale Toulouse Midi-Pyrénées-Centre National de la Recherche Scientifique (CNRS)-Université Toulouse III - Paul Sabatier (UT3), Université Fédérale Toulouse Midi-Pyrénées-Institut National des Sciences Appliquées - Toulouse (INSA Toulouse), Institut National des Sciences Appliquées (INSA)-Institut National des Sciences Appliquées (INSA)-Institut National Polytechnique (Toulouse) (Toulouse INP), School of Physical Sciences, University of Kent, Service Instrumentation Conception Caractérisation (LAAS-I2C), Université Fédérale Toulouse Midi-Pyrénées-Université Toulouse - Jean Jaurès (UT2J)-Université Toulouse 1 Capitole (UT1), Équipe Microsystèmes électromécaniques (LAAS-MEMS), Institut de Chimie de Toulouse (ICT), Institut de Recherche pour le Développement (IRD)-Université Toulouse III - Paul Sabatier (UT3), Université de Toulouse (UT)-Université de Toulouse (UT)-Institut de Chimie du CNRS (INC)-Centre National de la Recherche Scientifique (CNRS)-Institut National Polytechnique (Toulouse) (Toulouse INP), Université de Toulouse (UT)-Institut de Recherche pour le Développement (IRD)-Université Toulouse III - Paul Sabatier (UT3), Université de Toulouse (UT)-Centre National de la Recherche Scientifique (CNRS), Université de Toulouse (UT), Université Toulouse Capitole (UT Capitole), Université de Toulouse (UT)-Université de Toulouse (UT)-Institut National des Sciences Appliquées - Toulouse (INSA Toulouse), Institut National des Sciences Appliquées (INSA)-Université de Toulouse (UT)-Institut National des Sciences Appliquées (INSA)-Université Toulouse - Jean Jaurès (UT2J), Université de Toulouse (UT)-Université Toulouse III - Paul Sabatier (UT3), Université de Toulouse (UT)-Centre National de la Recherche Scientifique (CNRS)-Institut National Polytechnique (Toulouse) (Toulouse INP), and Université de Toulouse (UT)-Université Toulouse Capitole (UT Capitole)
Subjects: Spin states, Physical and chemical processes, Thin films, Young's modulus, 02 engineering and technology, Crystal structure, Inelastic scattering, 010402 general chemistry, Quantum mechanics, 01 natural sciences, Biochemistry, Catalysis, symbols.namesake, Colloid and Surface Chemistry, Spin crossover, [CHIM.COOR]Chemical Sciences/Coordination chemistry, QD, Young’s modulus, Anisotropy, Elastic modulus, QC, Bulk modulus, Condensed matter physics, Chemistry, Lattices, General Chemistry, 021001 nanoscience & nanotechnology, 0104 chemical sciences, symbols, 0210 nano-technology
Abstract: International audience; Molecular spin crossover complexes are promising candidates for mechanical actuation purposes. The relationships between their crystal structure and mechanical properties remain, however, not well understood. In this study, combining high pressure synchrotron X-ray diffraction, nuclear inelastic scattering, and micromechanical measurements, we assessed the effective macroscopic bulk modulus (B = 11.5 ± 1.5 GPa), Young’s modulus (Y = 10.9 ± 1.0 GPa), and Poisson’s ratio (ν = 0.34 ± 0.04) of the spin crossover complex [FeII(HB(tz)3)2] (tz = 1,2,4-triazol-1-yl). Crystal structure analysis revealed a pronounced anisotropy of the lattice compressibility, which was correlated with the difference in spacing between the molecules as well as by the distribution of the stiffest C–H···N interactions in different crystallographic directions. Switching the molecules from the low spin to the high spin state leads to a remarkable drop of the Young’s modulus to 7.1 ± 0.5 GPa both in bulk and thin film samples. The results highlight the application potential of these films in terms of strain (ε = −0.17 ± 0.05%), recoverable stress (σ = −21 ± 1 MPa), and work density (W/V = 15 ± 6 mJ/cm3).
Published: 2018

22. Unprecedented Reaction Mode of Phosphorus in Phosphinidene Rare-Earth Complexes: A Joint Experimental-Theoretical Study

Author: Haiwen Tian, Iker del Rosal, Kai Wang, Jianquan Hong, Laurent Maron, Xigeng Zhou, Lixin Zhang, Fudan University [Shanghai], Fudan Univ, Dept Mat Sci, Shanghai 200433, Peoples R China, Laboratoire de physique et chimie des nano-objets (LPCNO), Institut National des Sciences Appliquées - Toulouse (INSA Toulouse), Institut National des Sciences Appliquées (INSA)-Université de Toulouse (UT)-Institut National des Sciences Appliquées (INSA)-Université de Toulouse (UT)-Institut de Chimie de Toulouse (ICT), Institut de Recherche pour le Développement (IRD)-Université Toulouse III - Paul Sabatier (UT3), Université de Toulouse (UT)-Université de Toulouse (UT)-Institut de Chimie du CNRS (INC)-Centre National de la Recherche Scientifique (CNRS)-Institut National Polytechnique (Toulouse) (Toulouse INP), Université de Toulouse (UT)-Institut de Recherche pour le Développement (IRD)-Université Toulouse III - Paul Sabatier (UT3), Université de Toulouse (UT)-Institut de Chimie du CNRS (INC)-Centre National de la Recherche Scientifique (CNRS)-Institut National Polytechnique (Toulouse) (Toulouse INP), Université de Toulouse (UT)-Institut de Recherche sur les Systèmes Atomiques et Moléculaires Complexes (IRSAMC), Université Toulouse III - Paul Sabatier (UT3), Université de Toulouse (UT)-Université de Toulouse (UT)-Centre National de la Recherche Scientifique (CNRS)-Centre National de la Recherche Scientifique (CNRS), 973 program [2015CB856600], HPCs CALcul en Midi-Pyrenees (CALMIP-EOS grant) [1415], and National Natural Science Foundation of China [21672038, 21372047, 21732007]
Subjects: 010405 organic chemistry, Chemistry, Ligand, Isocyanide, General Chemistry, 010402 general chemistry, 01 natural sciences, Biochemistry, Medicinal chemistry, Catalysis, 0104 chemical sciences, Metal, chemistry.chemical_compound, Colloid and Surface Chemistry, Phenylacetylene, Phosphinidene, visual_art, visual_art.visual_art_medium, Density functional theory, [PHYS.PHYS.PHYS-CHEM-PH]Physics [physics]/Physics [physics]/Chemical Physics [physics.chem-ph], Bond cleavage, Carbodiimide
Abstract: International audience; Reactions of trinuclear rare-earth metal complexes bearing functionalized phosphinidene ligand [L(3)Ln(3)(mu(2)-Me)(2)(mu(3)-Me) (mu(3)-eta(1): eta(2):eta(2)-PC6H4-o) (L = [PhC((NC6H4Pr2)-Pr-i-2,6)(2)](-), Ln = Y (la), Lu (lb)) with phenylacetylene, CO2, diisopropyl carbodiimide, isocya-nide, or PhSSPh lead to the formation of a series of phosphorus-containing products. The reaction of 1 with CS2 yields two novel P-methyl-phosphindole-2,3-dithio-late dianion complexes, revealing an unusual tandem desulfurization/coupling/cyclization reaction mode of CS2. A possible reaction pathway was determined by density functional theory calculations. This emphasizes the key role of the reduction power of the formal P2- part of the phosphinidene in the C-S bond cleavage.
Published: 2017

23. Reversible Insertion of a C═C Bond into Magnesium(I) Dimers: Generation of Highly Active 1,2-Dimagnesioethane Compounds

Author: Cameron Jones, Carlos Alvarez Lamsfus, Ashlea Carroll, Aaron J. Boutland, Laurent Maron, Andreas Stasch, Monash University [Melbourne], Laboratoire de physique et chimie des nano-objets (LPCNO), Institut de Recherche sur les Systèmes Atomiques et Moléculaires Complexes (IRSAMC), Institut National des Sciences Appliquées - Toulouse (INSA Toulouse), Institut National des Sciences Appliquées (INSA)-Institut National des Sciences Appliquées (INSA)-Centre National de la Recherche Scientifique (CNRS)-Université Toulouse III - Paul Sabatier (UT3), Université Fédérale Toulouse Midi-Pyrénées-Université Fédérale Toulouse Midi-Pyrénées-Institut National des Sciences Appliquées - Toulouse (INSA Toulouse), Université Fédérale Toulouse Midi-Pyrénées-Université Fédérale Toulouse Midi-Pyrénées-Institut de Chimie de Toulouse (ICT-FR 2599), Institut National Polytechnique (Toulouse) (Toulouse INP), Université Fédérale Toulouse Midi-Pyrénées-Université Fédérale Toulouse Midi-Pyrénées-Centre National de la Recherche Scientifique (CNRS)-Institut de Recherche pour le Développement (IRD)-Université Toulouse III - Paul Sabatier (UT3), Université Fédérale Toulouse Midi-Pyrénées-Institut de Chimie du CNRS (INC)-Institut National Polytechnique (Toulouse) (Toulouse INP), Université Fédérale Toulouse Midi-Pyrénées-Centre National de la Recherche Scientifique (CNRS)-Institut de Recherche pour le Développement (IRD)-Institut de Chimie du CNRS (INC), University of St Andrews [Scotland], Institut National des Sciences Appliquées (INSA)-Université de Toulouse (UT)-Institut National des Sciences Appliquées (INSA)-Université de Toulouse (UT)-Institut de Chimie de Toulouse (ICT), Institut de Recherche pour le Développement (IRD)-Université Toulouse III - Paul Sabatier (UT3), Université de Toulouse (UT)-Université de Toulouse (UT)-Institut de Chimie du CNRS (INC)-Centre National de la Recherche Scientifique (CNRS)-Institut National Polytechnique (Toulouse) (Toulouse INP), Université de Toulouse (UT)-Institut de Recherche pour le Développement (IRD)-Université Toulouse III - Paul Sabatier (UT3), Université de Toulouse (UT)-Institut de Chimie du CNRS (INC)-Centre National de la Recherche Scientifique (CNRS)-Institut National Polytechnique (Toulouse) (Toulouse INP), Université de Toulouse (UT)-Institut de Recherche sur les Systèmes Atomiques et Moléculaires Complexes (IRSAMC), Université Toulouse III - Paul Sabatier (UT3), Université de Toulouse (UT)-Université de Toulouse (UT)-Centre National de la Recherche Scientifique (CNRS)-Centre National de la Recherche Scientifique (CNRS), and University of St Andrews. School of Chemistry
Subjects: [PHYS]Physics [physics], Ethylene, 010405 organic chemistry, Chemistry, Magnesium, chemistry.chemical_element, DAS, General Chemistry, QD Chemistry, 010402 general chemistry, 01 natural sciences, Biochemistry, Redox, Catalysis, 0104 chemical sciences, Metal, chemistry.chemical_compound, Colloid and Surface Chemistry, visual_art, Polymer chemistry, visual_art.visual_art_medium, [CHIM]Chemical Sciences, QD, Reactivity (chemistry)
Abstract: bibtex: ISI:000418783600015 bibtex\location:'1155 16TH ST, NW, WASHINGTON, DC 20036 USA',publisher:'AMER CHEMICAL SOC',type:'Article',affiliation:'Jones, C (Reprint Author), Monash Univ, Sch Chem, POB 23, Melbourne, Vic 3800, Australia. Maron, L (Reprint Author), Univ Toulouse, 135 Ave Rangueil, F-31077 Toulouse, France. Maron, L (Reprint Author), UPS, INSA, CNRS, LPCNO,UMR 5215, 135 Ave Rangueil, F-31077 Toulouse, France. Boutland, Aaron J.; Carroll, Ashlea; Stasch, Andreas; Jones, Cameron, Monash Univ, Sch Chem, POB 23, Melbourne, Vic 3800, Australia. Lamsfus, Carlos Alvarez; Maron, Laurent, Univ Toulouse, 135 Ave Rangueil, F-31077 Toulouse, France. Lamsfus, Carlos Alvarez; Maron, Laurent, UPS, INSA, CNRS, LPCNO,UMR 5215, 135 Ave Rangueil, F-31077 Toulouse, France. Stasch, Andreas, Univ St Andrews, EaStCHEM Sch Chem, St Andrews KY16 9ST, Fife, Scotland.','author-email':'laurent.maron@irsamc.ups-tlse.fr cameron.jones@monash.edu',da:'2018-12-05','doc-delivery-number':'FR0WB','funding-acknowledgement':'Australian Research Council; Chinese Academy of Science; U.S. Air Force Asian Office of Aerospace Research and Development [FA2386-14-1-4043]; Alexander von Humboldt Foundation','funding-text':'Financial support from the Australian Research Council (C.J.), the U.S. Air Force Asian Office of Aerospace Research and Development (grant FA2386-14-1-4043 to C.J.), The Alexander von Humboldt Foundation (L.M.), and the Chinese Academy of Science (L.M.) is acknowledged.','journal-iso':'J. Am. Chem. Soc.','keywords-plus':'MAIN-GROUP ELEMENTS; AMBIENT CONDITIONS; ETHYLENE; COMPLEXES; CYCLOADDITION; REACTIVITY; ACTIVATION; MOLECULES; CATALYSIS; SILYLENE','number-of-cited-references':'33','orcid-numbers':'Stasch, Andreas/0000-0002-7407-8287','research-areas':'Chemistry','times-cited':'5','unique-id':'ISI:000418783600015','usage-count-last-180-days':'8','usage-count-since-2013':'26','web-of-science-categories':'Chemistry, Multidisciplinary'\; International audience; The insertion of 1,1-diphenylethylene into the Mg-Mg bond of two magnesium(I) dimers, [((Ar)Nacnac)Mg-](2) (Ar = C6H2Me3-2,4,6 (Mes); C6H3Et2-2,6 (Dep)), yielding 1,2-dimagnesioethane products, [\((Ar)Nacnac)Mg\(2)(mu-CH2CPh2)], is described. These reactions are readily reversible at room temperature and thus represent the first examples of room-temperature reversible redox processes for s-block metal complexes. The 1,2-dimagnesioethane products are highly activated magnesium alkyls and Show unprecedented, uncatalyted reactivity toward H-2, CO, and ethylene. Computational studies have investigated the mechanisms of all presented reaction types.
Published: 2017

24. Activation of CO by Hydrogenated Magnesium(I) Dimers: Sterically Controlled Formation of Ethenediolate and Cyclopropanetriolate Complexes

Author: Ralte Lalrempuia, Laurent Maron, Simon J. Bonyhady, Benedikt Schwarze, Andreas Stasch, Christos E. Kefalidis, Cameron Jones, School of Chemistry, Monash University, 3800 Clayton, Victoria (Australie), Monash University [Clayton], Laboratoire de physique et chimie des nano-objets (LPCNO), Institut National des Sciences Appliquées - Toulouse (INSA Toulouse), Institut National des Sciences Appliquées (INSA)-Université de Toulouse (UT)-Institut National des Sciences Appliquées (INSA)-Université de Toulouse (UT)-Institut de Chimie de Toulouse (ICT), Institut de Recherche pour le Développement (IRD)-Université Toulouse III - Paul Sabatier (UT3), Université de Toulouse (UT)-Université de Toulouse (UT)-Institut de Chimie du CNRS (INC)-Centre National de la Recherche Scientifique (CNRS)-Institut National Polytechnique (Toulouse) (Toulouse INP), Université de Toulouse (UT)-Institut de Recherche pour le Développement (IRD)-Université Toulouse III - Paul Sabatier (UT3), Université de Toulouse (UT)-Institut de Chimie du CNRS (INC)-Centre National de la Recherche Scientifique (CNRS)-Institut National Polytechnique (Toulouse) (Toulouse INP), Université de Toulouse (UT)-Institut de Recherche sur les Systèmes Atomiques et Moléculaires Complexes (IRSAMC), Université Toulouse III - Paul Sabatier (UT3), Université de Toulouse (UT)-Université de Toulouse (UT)-Centre National de la Recherche Scientifique (CNRS)-Centre National de la Recherche Scientifique (CNRS), School of Chemistry, Monash UniVersity, Clayton, VIC. 3800 (Australia), Institut de Recherche sur les Systèmes Atomiques et Moléculaires Complexes (IRSAMC), Institut National des Sciences Appliquées (INSA)-Institut National des Sciences Appliquées (INSA)-Centre National de la Recherche Scientifique (CNRS)-Université Toulouse III - Paul Sabatier (UT3), Université Fédérale Toulouse Midi-Pyrénées-Université Fédérale Toulouse Midi-Pyrénées-Institut National des Sciences Appliquées - Toulouse (INSA Toulouse), Université Fédérale Toulouse Midi-Pyrénées-Université Fédérale Toulouse Midi-Pyrénées-Institut de Chimie de Toulouse (ICT-FR 2599), Institut National Polytechnique (Toulouse) (Toulouse INP), Université Fédérale Toulouse Midi-Pyrénées-Université Fédérale Toulouse Midi-Pyrénées-Centre National de la Recherche Scientifique (CNRS)-Institut de Recherche pour le Développement (IRD)-Université Toulouse III - Paul Sabatier (UT3), Université Fédérale Toulouse Midi-Pyrénées-Institut de Chimie du CNRS (INC)-Institut National Polytechnique (Toulouse) (Toulouse INP), and Université Fédérale Toulouse Midi-Pyrénées-Centre National de la Recherche Scientifique (CNRS)-Institut de Recherche pour le Développement (IRD)-Institut de Chimie du CNRS (INC)
Subjects: Steric effects, 010405 organic chemistry, Chemistry, Hydride, Magnesium, Inorganic chemistry, chemistry.chemical_element, NacNac, General Chemistry, 010402 general chemistry, 01 natural sciences, Biochemistry, Medicinal chemistry, Catalysis, 0104 chemical sciences, Metal, chemistry.chemical_compound, Colloid and Surface Chemistry, visual_art, visual_art.visual_art_medium, [PHYS.PHYS.PHYS-CHEM-PH]Physics [physics]/Physics [physics]/Chemical Physics [physics.chem-ph], Co activation, Oxygenate
Abstract: International audience; This study details the formal hydrogenation of two magnesium(I) dimers {(Nacnac)Mg}2 (Nacnac = [{(C6H3R2-2,6)NCMe}2CH]−; R = Pri (DipNacnac), Et (DepNacnac)) using 1,3-cyclohexadiene. These reactions afford the magnesium(II) hydride complexes, {(Nacnac)Mg(μ-H)}2. Their reactions with excess CO are sterically controlled and lead cleanly to different C–C coupled products, viz. the ethenediolate complex, (DipNacnac)Mg{κ1-O-[(DipNacnac)Mg(κ2-O,O-O2C2H2)]}, and the first cyclopropanetriolate complex of any metal, cis-{(DepNacnac)Mg}3{μ-C3(H3)O3}. Computational studies imply the CO activation processes proceed via very similar mechanisms to those previously reported for related reactions involving f-block metal hydride compounds. This work highlights the potential magnesium compounds hold for use in the “Fischer–Tropsch-like” transformation of CO/H2 mixtures to value added oxygenate products.
Published: 2015

25. Electronic Structure and Properties of Berkelium Iodates

Author: Teresa M. Eaton, Gustavo E. Scuseria, Cristian Celis-Barros, Gregory A. Galmin, Paul Kögerler, Ronald J. Clark, Alexandra A. Arico, Matthew L. Marsh, Lambertus J. van de Burgt, Kevin Seidler, Manfred Speldrich, Kuan-Wen Chen, Frédéric Gendron, Alejandro J. Garza, Alexander T. Chemey, David E. Hobart, Ramiro Arratia-Pérez, Shane S. Galley, Ashley L. Gray, Jason A. Johnson, Jochen Autschbach, Laurent Maron, Ryan Baumbach, Dayán Páez-Hernández, Jamie C. Wang, Mark A. Silver, Kenneth Hanson, Thomas E. Albrecht-Schmitt, Shelley M. Van Cleve, Michael Ruf, Samantha K. Cary, Florida State University [Tallahassee] (FSU), Department of Chemistry and Biochemistry, Tallahassee (DCB), National High Magnetic Field Laboratory (NHMFL), FSU, Department of Chemistry and Biochemistry, and National High Magnetic Field Laboratory, Environmental Health and Safety, Nuclear Materials Processing Group [Oak Ridge], Oak Ridge National Laboratory [Oak Ridge] (ORNL), UT-Battelle, LLC-UT-Battelle, LLC, Department of Chemistry [Buffalo], University at Buffalo [SUNY] (SUNY Buffalo), State University of New York (SUNY)-State University of New York (SUNY), Department of Chemistry [Houston], Rice University [Houston], Laboratoire de physique et chimie des nano-objets (LPCNO), Institut de Recherche sur les Systèmes Atomiques et Moléculaires Complexes (IRSAMC), Institut National des Sciences Appliquées - Toulouse (INSA Toulouse), Institut National des Sciences Appliquées (INSA)-Institut National des Sciences Appliquées (INSA)-Centre National de la Recherche Scientifique (CNRS)-Université Toulouse III - Paul Sabatier (UT3), Université Fédérale Toulouse Midi-Pyrénées-Université Fédérale Toulouse Midi-Pyrénées-Institut National des Sciences Appliquées - Toulouse (INSA Toulouse), Université Fédérale Toulouse Midi-Pyrénées-Université Fédérale Toulouse Midi-Pyrénées-Institut de Chimie de Toulouse (ICT-FR 2599), Institut National Polytechnique (Toulouse) (Toulouse INP), Université Fédérale Toulouse Midi-Pyrénées-Université Fédérale Toulouse Midi-Pyrénées-Centre National de la Recherche Scientifique (CNRS)-Institut de Recherche pour le Développement (IRD)-Université Toulouse III - Paul Sabatier (UT3), Université Fédérale Toulouse Midi-Pyrénées-Institut de Chimie du CNRS (INC)-Institut National Polytechnique (Toulouse) (Toulouse INP), Université Fédérale Toulouse Midi-Pyrénées-Centre National de la Recherche Scientifique (CNRS)-Institut de Recherche pour le Développement (IRD)-Institut de Chimie du CNRS (INC), Institut für Anorganische Chemie, Rheinisch-Westfälische Technische Hochschule Aachen (RWTH), Centro de NanoCiencias Aplicadas [Santiago] (CANS), Universidad Andrés Bello [Santiago] (UNAB), Bruker AXS, Institut National des Sciences Appliquées (INSA)-Université de Toulouse (UT)-Institut National des Sciences Appliquées (INSA)-Université de Toulouse (UT)-Institut de Chimie de Toulouse (ICT), Institut de Recherche pour le Développement (IRD)-Université Toulouse III - Paul Sabatier (UT3), Université de Toulouse (UT)-Université de Toulouse (UT)-Institut de Chimie du CNRS (INC)-Centre National de la Recherche Scientifique (CNRS)-Institut National Polytechnique (Toulouse) (Toulouse INP), Université de Toulouse (UT)-Institut de Recherche pour le Développement (IRD)-Université Toulouse III - Paul Sabatier (UT3), Université de Toulouse (UT)-Institut de Chimie du CNRS (INC)-Centre National de la Recherche Scientifique (CNRS)-Institut National Polytechnique (Toulouse) (Toulouse INP), Université de Toulouse (UT)-Institut de Recherche sur les Systèmes Atomiques et Moléculaires Complexes (IRSAMC), Université Toulouse III - Paul Sabatier (UT3), Université de Toulouse (UT)-Université de Toulouse (UT)-Centre National de la Recherche Scientifique (CNRS)-Centre National de la Recherche Scientifique (CNRS), and Rheinisch-Westfälische Technische Hochschule Aachen University (RWTH)
Subjects: Lanthanide, [PHYS]Physics [physics], Ionic radius, Photoluminescence, Absorption spectroscopy, 010405 organic chemistry, Inorganic chemistry, General Chemistry, 010402 general chemistry, 01 natural sciences, Biochemistry, Catalysis, 0104 chemical sciences, 3. Good health, Bond length, Crystallography, chemistry.chemical_compound, Colloid and Surface Chemistry, chemistry, ddc:540, [CHIM]Chemical Sciences, Absorption (chemistry), Luminescence, Iodate
Abstract: bibtex: ISI:000412043000020 bibtex\location:'1155 16TH ST, NW, WASHINGTON, DC 20036 USA',publisher:'AMER CHEMICAL SOC',type:'Article',affiliation:'Albrecht-Schmitt, TE (Reprint Author), Florida State Univ, Dept Chem & Biochem, Tallahassee, FL 32306 USA. Silver, Mark A.; Cary, Samantha K.; Arico, Alexandra A.; Galmin, Gregory A.; Wang, Jamie C.; Clark, Ronald J.; Chemey, Alexander; Eaton, Teresa M.; Marsh, Matthew L.; Seidler, Kevin; Galley, Shane S.; van de Burgt, Lambertus; Hobart, David E.; Hanson, Kenneth; Albrecht-Schmitt, Thomas E., Florida State Univ, Dept Chem & Biochem, Tallahassee, FL 32306 USA. Garza, Alejandro J.; Scuseria, Gustavo E., Rice Univ, Dept Chem, POB 1892, Houston, TX 77251 USA. Baumbach, Ryan E.; Chen, Kuan-Wen, Natl High Magnet Field Lab, Tallahassee, FL 32310 USA. Johnson, Jason A.; Gray, Ashley L., Florida State Univ, Environm Hlth & Safety, Tallahassee, FL 32306 USA. Van Cleve, Shelley M., Oak Ridge Natl Lab, Nucl Mat Proc Grp, One Bethel Valley Rd, Oak Ridge, TN 37830 USA. Gendron, Frederic; Autschbach, Jochen, Univ Buffalo State Univ New York, Dept Chem, Buffalo, NY 14260 USA. Maron, Laurent, Inst Natl Sci Appl, Lab Phys & Chim Nanoobjets, F-31077 Toulouse 4, France. Speldrich, Manfred; Koegerler, Paul, Rhein Westfal TH Aachen, Inst Anorgan Chem, D-52074 Aachen, Germany. Celis-Barros, Cristian; Paez-Hernandez, Dayan; Arratia-Perez, Ramiro, Univ Andres Bello, Fac Ciencias Exactas, Ctr Nanociencias Aplicadas, Republ 275, Santiago, Chile. Ruf, Michael, Bruker AXS, 5465 East Cheryl Pkwy, Madison, WI 53711 USA.','author-email':'albrecht-schinitt@chem.fsu.edu',da:'2018-12-05','doc-delivery-number':'FI5SB','funding-acknowledgement':'U.S. Department of Energy, Office of Science, Office of Basic Energy Sciences, Heavy Elements Chemistry Program [DE-FG02-13ER16414, DE-SC0001136, DE-FG02-04ER15523]; Welch Foundation Chair [C-0036]; National Science Foundation [DMR-1157490, DGE-1449440]; State of Florida; U.S. Department of Energy; CBFO Fellowship Program (MAS) - U.S. Department of Energy','funding-text':'This material is based upon work supported by the U.S. Department of Energy, Office of Science, Office of Basic Energy Sciences, Heavy Elements Chemistry Program, under Award Numbers DE-FG02-13ER16414 (FSU), DE-SC0001136 (formerly DE-FG02-09ER16066) (FG & JA), and DE-FG02-04ER15523 (G.E.S). G.E.S. is a Welch Foundation Chair (Grant No. C-0036). The isotopes used in this research were supplied by the U.S. Department of Energy, Office of Science, by the Isotope Program in the Office of Nuclear Physics. The \textlessSUP\textgreater249\textless/SUP\textgreaterBk was provided to Florida State University by the Isotope Development and Production for Research and Applications Program through the Radiochemical Engineering and Development Center at Oak Ridge National Laboratory. Magnetization measurements using the VSM SQUID MPMS were performed at the National High Magnetic Field Laboratory, which is supported by National Science Foundation Cooperative Agreement No. DMR-1157490, the State of Florida, and the U.S. Department of Energy. This research is supported in part by an appointment to the CBFO Fellowship Program (MAS), sponsored by the U.S. Department of Energy and administered by the Oak Ridge Institute for Science and Education. Jamie Wang is supported by the National Science Foundation Graduate Research Fellowship under Grant No. DGE-1449440.','journal-iso':'J. Am. Chem. Soc.','keywords-plus':'VALENCE BASIS-SETS; ENERGY-ADJUSTED PSEUDOPOTENTIALS; MOLECULAR-ORBITAL METHODS; CRYSTAL-STRUCTURE; AB-INITIO; MAGNETIC-SUSCEPTIBILITY; COORDINATION GEOMETRY; PERTURBATION-THEORY; IONIC-RADII; PLUTONIUM','number-of-cited-references':'113',oa:'Bronze','orcid-numbers':'Kogerler, Paul/0000-0001-7831-3953 Gendron, Frederic/0000-0002-1896-3978 Hanson, Kenneth/0000-0001-7219-7808 Albrecht-Schmitt, Thomas/0000-0002-2989-3311 Chemey, Alexander/0000-0002-0679-7845 Paez, Dayan/0000-0003-2747-9982 Speldrich, Manfred/0000-0002-8626-6410 Celis-Barros, Cristian/0000-0002-4685-5229 Garza, Alejandro/0000-0001-6995-2833','research-areas':'Chemistry','researcherid-numbers':'Kogerler, Paul/H-5866-2013','times-cited':'5','unique-id':'ISI:000412043000020','usage-count-last-180-days':'8','usage-count-since-2013':'36','web-of-science-categories':'Chemistry, Multidisciplinary'\; International audience; The reaction of Bk-249(OH)(4) with iodate under hydro thermal conditions results in the formation of Bk(IO3)(3) as the major product with trace amounts of Bk(IO3)(4) also crystallizing from the reaction mixture. The structure of Bk(Io(3))(3) consists of nine-coordinate BO cations that are bridged by iodate anions to yield layers that are isomorphous with those found for Am-III, Cf-III, and with lanthanides that possess similar ionic radii. Bk(IO3)(4) was expected to adopt the same structure as M(IO3)(4) (M = Ce, Np, Pu), but instead parallels the structural chemistry of the smaller Zr-IV cation. Bk-III-O and Bk-IV-O bond lengths are shorter than anticipated and provide further support for a postcurium break in the actinide series. Photoluminescence and absorption spectra collected from single crystals of Bk(IO3)(4) show evidence for doping with Bkill in these crystals. In addition to luminescence from Bkul in the Bk(IO3)(4) crystals, a broad-band absorption feature is initially present that is similar to features observed in systems with intervalence charge transfer. However, the high-specific activity of Bk-249 (t(1/2) = 320 d) causes oxidation of Bk-III and only Bk-IV is present after a few days with concomitant loss of both the Bk-III luminescence and the broadband feature. The electronic structure of Bk(IO3)(3) and Bk(IO3)(4) were examined using a range of computational methods that include density functional theory both on clusters and on periodic structures, relativistic ab initio wave function calculations that incorporate spin orbit coupling (CASSCF), and by a full-model Hamiltonian with spin-orbit coupling and Slater-Condon parameters (CONDON). Some of these methods provide evidence for an asymmetric ground state present in Bk-IV that does not strictly adhere to Russel Saunders coupling and Hund's Rule even though it possesses a half-filled Sf(7) shell. Multiple factors contribute. to the asymmetry that include 5f electrons being present in microstates that are not solely spin up, spin-orbit coupling induced mixing of low-lying excited states with the ground state, and covalency in the Bk-IV-O bonds that distributes the 5f electrons onto the ligands. These factors are absent or diminished in other f(7) ions such as Gd-III or Cm-III.
Published: 2017

26. Facile Oxidative Addition of Aryl Iodides to Gold(I) by Ligand Design: Bending Turns on Reactivity

Author: Karinne Miqueu, Maximilian Joost, Sonia Ladeira, Abdallah Zeineddine, Didier Bourissou, Abderrahmane Amgoune, Laura Estévez, Laboratoire Hétérochimie Fondamentale et Appliquée (LHFA), Université Toulouse III - Paul Sabatier (UT3), Université Fédérale Toulouse Midi-Pyrénées-Université Fédérale Toulouse Midi-Pyrénées-Centre National de la Recherche Scientifique (CNRS)-Institut de Chimie du CNRS (INC)-Institut de Chimie de Toulouse (ICT-FR 2599), Institut National Polytechnique (Toulouse) (Toulouse INP), Université Fédérale Toulouse Midi-Pyrénées-Université Fédérale Toulouse Midi-Pyrénées-Centre National de la Recherche Scientifique (CNRS)-Institut de Recherche pour le Développement (IRD)-Université Toulouse III - Paul Sabatier (UT3), Université Fédérale Toulouse Midi-Pyrénées-Institut de Chimie du CNRS (INC)-Institut National Polytechnique (Toulouse) (Toulouse INP), Université Fédérale Toulouse Midi-Pyrénées-Centre National de la Recherche Scientifique (CNRS)-Institut de Recherche pour le Développement (IRD), Institut des sciences analytiques et de physico-chimie pour l'environnement et les materiaux (IPREM), and Centre National de la Recherche Scientifique (CNRS)-Institut de Chimie du CNRS (INC)-Université de Pau et des Pays de l'Adour (UPPA)
Subjects: 010405 organic chemistry, Ligand, Aryl, General Chemistry, Bending, 010402 general chemistry, Photochemistry, 01 natural sciences, Biochemistry, Oxidative addition, Catalysis, 0104 chemical sciences, chemistry.chemical_compound, Colloid and Surface Chemistry, chemistry, Polymer chemistry, [CHIM]Chemical Sciences, Reactivity (chemistry)
Abstract: International audience; Thanks to rational ligand design, the first gold(I) complexes to undergo oxidative addition of aryl iodides were discovered. The reaction proceeds under mild conditions and is general. The ensuing aryl gold(III) complexes have been characterized by spectroscopic and crystallographic means. DFT calculations indicate that the bending induced by the diphosphine ligand plays a key role in this process. © 2014 American Chemical Society.
Published: 2014

27. An Oxysulfate Fe2O(SO4)2 Electrode for Sustainable Li-Based Batteries

Author: Marie-Liesse Doublet, Moulay Tahar Sougrati, Artem M. Abakumov, Matthieu Courty, Gwenaëlle Rousse, Gustaaf Van Tendeloo, Meiling Sun, Jean-Marie Tarascon, Réseau sur le stockage électrochimique de l'énergie (RS2E), Université de Nantes (UN)-Aix Marseille Université (AMU)-Université de Haute-Alsace (UHA) Mulhouse - Colmar (Université de Haute-Alsace (UHA))-Collège de France (CdF (institution))-Université de Picardie Jules Verne (UPJV)-Ecole Nationale Supérieure de Chimie de Montpellier (ENSCM)-Ecole Nationale Supérieure de Chimie de Paris - Chimie ParisTech-PSL (ENSCP), Université Paris sciences et lettres (PSL)-Université Paris sciences et lettres (PSL)-Université de Pau et des Pays de l'Adour (UPPA)-Institut de Chimie du CNRS (INC)-Université de Montpellier (UM)-Sorbonne Université (SU)-Centre National de la Recherche Scientifique (CNRS)-Institut National Polytechnique (Toulouse) (Toulouse INP), Université de Toulouse (UT)-Université de Toulouse (UT)-Institut polytechnique de Grenoble - Grenoble Institute of Technology (Grenoble INP ), Université Grenoble Alpes (UGA)-Université Grenoble Alpes (UGA), Université Pierre et Marie Curie - Paris 6 (UPMC), Institut Charles Gerhardt Montpellier - Institut de Chimie Moléculaire et des Matériaux de Montpellier (ICGM ICMMM), Université Montpellier 1 (UM1)-Université Montpellier 2 - Sciences et Techniques (UM2)-Ecole Nationale Supérieure de Chimie de Montpellier (ENSCM)-Institut de Chimie du CNRS (INC)-Centre National de la Recherche Scientifique (CNRS), Collège de France - Chaire Chimie du solide et énergie, Chimie du solide et de l'énergie (CSE), Collège de France (CdF (institution))-Institut de Chimie du CNRS (INC)-Sorbonne Université (SU)-Centre National de la Recherche Scientifique (CNRS)-Collège de France (CdF (institution))-Institut de Chimie du CNRS (INC)-Sorbonne Université (SU)-Centre National de la Recherche Scientifique (CNRS), RS2E, Université de Picardie Jules Verne (UPJV)-Institut de Chimie du CNRS (INC)-Aix Marseille Université (AMU)-Université de Pau et des Pays de l'Adour (UPPA)-Université de Nantes (UN)-Université de Montpellier (UM)-Centre National de la Recherche Scientifique (CNRS)-Sorbonne Université (SU)-Ecole Nationale Supérieure de Chimie de Paris - Chimie ParisTech-PSL (ENSCP), Université Paris sciences et lettres (PSL)-Université Paris sciences et lettres (PSL)-Université de Haute-Alsace (UHA) Mulhouse - Colmar (Université de Haute-Alsace (UHA))-Collège de France (CdF (institution))-Institut polytechnique de Grenoble - Grenoble Institute of Technology (Grenoble INP ), Université Grenoble Alpes (UGA)-Université Grenoble Alpes (UGA)-Institut National Polytechnique (Toulouse) (Toulouse INP), Université Fédérale Toulouse Midi-Pyrénées-Université Fédérale Toulouse Midi-Pyrénées-Ecole Nationale Supérieure de Chimie de Montpellier (ENSCM), Ecole Nationale Supérieure de Chimie de Montpellier (ENSCM)-Centre National de la Recherche Scientifique (CNRS)-Université de Montpellier (UM)-Université Montpellier 1 (UM1)-Université Montpellier 2 - Sciences et Techniques (UM2)-Institut de Chimie du CNRS (INC), Chaire Chimie du solide et énergie, and Centre National de la Recherche Scientifique (CNRS)-Collège de France (CdF (institution))-Institut de Chimie du CNRS (INC)-Sorbonne Université (SU)-Centre National de la Recherche Scientifique (CNRS)-Collège de France (CdF (institution))-Institut de Chimie du CNRS (INC)-Sorbonne Université (SU)
Subjects: Electrode material, Chemistry, Inorganic chemistry, Nanotechnology, 02 engineering and technology, General Chemistry, 010402 general chemistry, 021001 nanoscience & nanotechnology, 7. Clean energy, 01 natural sciences, Biochemistry, Redox, Catalysis, 0104 chemical sciences, Colloid and Surface Chemistry, Octahedron, Phase (matter), Electrode, [PHYS.COND.CM-MS]Physics [physics]/Condensed Matter [cond-mat]/Materials Science [cond-mat.mtrl-sci], 0210 nano-technology
Abstract: International audience; High-performing Fe-based electrodes for Li-based batteries are eagerly pursued because of the abundance and environmental benignity of iron, with especially great interest in polyanionic compounds because of their flexibility in tuning the Fe3+/Fe2+ redox potential. We report herein the synthesis and structure of a new Fe-based oxysulfate phase, Fe2O(SO4)2, made at low temperature from abundant elements, which electrochemically reacts with nearly 1.6 Li atoms at an average voltage of 3.0 V versus Li+/Li, leading to a sustained reversible capacity of ≈125 mAh/g. The Li insertion–deinsertion process, the first ever reported in any oxysulfate, entails complex phase transformations associated with the position of iron within the FeO6 octahedra. This finding opens a new path worth exploring in the quest for new positive electrode materials.
Published: 2014

28. Elucidation of the Na2/3FePO4 and Li2/3FePO4 Intermediate Superstructure Revealing a Pseudouniform Ordering in 2D

Author: Philippe Moreau, Dominique Guyomard, Marine Cuisinier, Florent Boucher, Joël Gaubicher, Institut des Matériaux Jean Rouxel (IMN), Université de Nantes - UFR des Sciences et des Techniques (UN UFR ST), Université de Nantes (UN)-Université de Nantes (UN)-Centre National de la Recherche Scientifique (CNRS)-Institut de Chimie du CNRS (INC)-Ecole Polytechnique de l'Université de Nantes (EPUN), Université de Nantes (UN)-Université de Nantes (UN), Réseau sur le stockage électrochimique de l'énergie (RS2E), Université de Picardie Jules Verne (UPJV)-Institut de Chimie du CNRS (INC)-Aix Marseille Université (AMU)-Université de Pau et des Pays de l'Adour (UPPA)-Université de Nantes (UN)-Université de Montpellier (UM)-Centre National de la Recherche Scientifique (CNRS)-Sorbonne Université (SU)-Ecole Nationale Supérieure de Chimie de Paris - Chimie ParisTech-PSL (ENSCP), Université Paris sciences et lettres (PSL)-Université Paris sciences et lettres (PSL)-Université de Haute-Alsace (UHA) Mulhouse - Colmar (Université de Haute-Alsace (UHA))-Collège de France (CdF (institution))-Institut polytechnique de Grenoble - Grenoble Institute of Technology (Grenoble INP ), Université Grenoble Alpes (UGA)-Université Grenoble Alpes (UGA)-Institut National Polytechnique (Toulouse) (Toulouse INP), Université Fédérale Toulouse Midi-Pyrénées-Université Fédérale Toulouse Midi-Pyrénées-Ecole Nationale Supérieure de Chimie de Montpellier (ENSCM), university hospital, University Hospital, Université de Nantes (UN)-Université de Nantes (UN)-Ecole Polytechnique de l'Université de Nantes (EPUN), Université de Nantes (UN)-Université de Nantes (UN)-Institut de Chimie du CNRS (INC)-Centre National de la Recherche Scientifique (CNRS), Université de Nantes (UN)-Aix Marseille Université (AMU)-Université de Haute-Alsace (UHA) Mulhouse - Colmar (Université de Haute-Alsace (UHA))-Collège de France (CdF (institution))-Université de Picardie Jules Verne (UPJV)-Ecole Nationale Supérieure de Chimie de Montpellier (ENSCM)-Ecole Nationale Supérieure de Chimie de Paris - Chimie ParisTech-PSL (ENSCP), Université Paris sciences et lettres (PSL)-Université Paris sciences et lettres (PSL)-Université de Pau et des Pays de l'Adour (UPPA)-Institut de Chimie du CNRS (INC)-Université de Montpellier (UM)-Sorbonne Université (SU)-Centre National de la Recherche Scientifique (CNRS)-Institut National Polytechnique (Toulouse) (Toulouse INP), Université de Toulouse (UT)-Université de Toulouse (UT)-Institut polytechnique de Grenoble - Grenoble Institute of Technology (Grenoble INP ), and Université Grenoble Alpes (UGA)-Université Grenoble Alpes (UGA)
Subjects: Chemistry, Intercalation (chemistry), 02 engineering and technology, General Chemistry, 010402 general chemistry, 021001 nanoscience & nanotechnology, 01 natural sciences, Biochemistry, Catalysis, 0104 chemical sciences, Crystallography, Colloid and Surface Chemistry, Metastability, Vacancy defect, Mössbauer spectroscopy, [PHYS.COND.CM-MS]Physics [physics]/Condensed Matter [cond-mat]/Materials Science [cond-mat.mtrl-sci], Supercell (crystal), 0210 nano-technology, Superstructure (condensed matter), ComputingMilieux_MISCELLANEOUS, Monoclinic crystal system, Electrochemical potential
Abstract: Based on TEM, synchrotron X-ray diffraction, DFT calculations, and Mossbauer spectroscopy, a unified understanding of the Na and Li intercalation process in FePO4 is proposed. The key to this lies in solving the highly sought-after intermediate A(2/3)FePO4 (A = Na, Li) superstructures that are characterized by alkali ions as well as Fe(II)/Fe(III) charge orderings in a monoclinic three-fold supercell. Formation energies and electrochemical potential calculations confirm that Na(2/3)FePO4 and Li(2/3)FePO4 are stable and metastable, respectively, and that they yield insertion potentials in fair agreement with experimental values. The 2/3 Na(Li) and 1/3 vacancy sublattice of the intermediate phases forms a dense (101)(Pnma) plane in which the atom/vacancy ordering is very similar to that predicted for the most uniform distribution of 1/3 of vacancies in a 2D square lattice. Structural analysis strongly suggests that the key role of this dense plane is to constrain the intercalation in the diffusion channels to operate by cooperative filling of (bc)(Pnma). From a practical point of view, this generalized mechanism highlights the fact that an interesting strategy for obtaining high-rate FePO4 materials would consist in designing grains with an enhanced (101) surface area, thereby offering potential for substantial improvements with respect to the performance of rechargeable Li and Na batteries.
Published: 2014

29. Activation of a σ-SnSn Bond at Copper, Followed by Double Addition to an Alkyne

Author: Sonia Mallet-Ladeira, Didier Bourissou, Karinne Miqueu, Nicolas Lassauque, Abderrahmane Amgoune, Pauline Gualco, Laboratoire Hétérochimie Fondamentale et Appliquée (LHFA), Université Toulouse III - Paul Sabatier (UT3), Université Fédérale Toulouse Midi-Pyrénées-Université Fédérale Toulouse Midi-Pyrénées-Centre National de la Recherche Scientifique (CNRS)-Institut de Chimie du CNRS (INC)-Institut de Chimie de Toulouse (ICT-FR 2599), Institut National Polytechnique (Toulouse) (Toulouse INP), Université Fédérale Toulouse Midi-Pyrénées-Université Fédérale Toulouse Midi-Pyrénées-Centre National de la Recherche Scientifique (CNRS)-Institut de Recherche pour le Développement (IRD)-Université Toulouse III - Paul Sabatier (UT3), Université Fédérale Toulouse Midi-Pyrénées-Institut de Chimie du CNRS (INC)-Institut National Polytechnique (Toulouse) (Toulouse INP), Université Fédérale Toulouse Midi-Pyrénées-Centre National de la Recherche Scientifique (CNRS)-Institut de Recherche pour le Développement (IRD), Institut de Chimie de Toulouse (ICT-FR 2599), Université Fédérale Toulouse Midi-Pyrénées-Institut de Chimie du CNRS (INC), Institut des sciences analytiques et de physico-chimie pour l'environnement et les materiaux (IPREM), and Université de Pau et des Pays de l'Adour (UPPA)-Institut de Chimie du CNRS (INC)-Centre National de la Recherche Scientifique (CNRS)
Subjects: chemistry.chemical_classification, [CHIM.ORGA]Chemical Sciences/Organic chemistry, 010405 organic chemistry, Stereochemistry, Alkyne, chemistry.chemical_element, [CHIM.CATA]Chemical Sciences/Catalysis, General Chemistry, 010402 general chemistry, 01 natural sciences, Biochemistry, Copper, Oxidative addition, Catalysis, 0104 chemical sciences, [CHIM.THEO]Chemical Sciences/Theoretical and/or physical chemistry, Crystallography, [CHIM.POLY]Chemical Sciences/Polymers, Colloid and Surface Chemistry, chemistry, Polar, [CHIM.COOR]Chemical Sciences/Coordination chemistry, Chelation
Abstract: cited By 19; International audience; Many synthetically useful copper-catalyzed transformations involve the activation of apolar or weakly polar σ-bonds (E-H and E-E′ bonds, with E = C, B, Si, Sn, etc.). Yet, little is known so far about the associated elementary steps, and it is highly desirable to gain better knowledge regarding the way σ-bonds can be activated by copper to help further development in this area. To this end, we became interested in investigating the coordination and activation of apolar or weakly polar σ-bonds at copper using chelating assistance. Here we report investigations of gold and copper complexes deriving from the diphosphine-stannane [Ph2P(o-C6H 4)Me2Sn-SnMe2(o-C6H 4)PPh2] 1. The σ-SnSn bond of 1 readily undergoes oxidative addition at both gold and copper, giving bis(stannyl) Au+ and Cu+ complexes 2 and 3. Coordination of 1 to CuBr leads to the neutral complex 4 which features more σ-SnSn complex character. The ability of complex 3 to undergo insertion reactions with alkynes was then examined. With methyl propiolate, a clean reaction occurred, and the bis-stannylated alkene copper complex 5 was isolated. The structures of ligand 1 and complexes 2-5 have been unambiguously determined by multinuclear NMR spectroscopy and crystallography. These results substantiate the ability of copper to promote the addition of apolar σ-bonds to CC multiple bonds via a 2e redox sequence and draw thereby an unprecedented parallel with the group 10 metals. © 2013 American Chemical Society.
Published: 2013

30. Donor-Stabilized Silacyclobutanone: A Precursor of 1-Silaketene via Retro-[2 + 2]-Cycloaddition Reaction at Room Temperature

Author: Vicenç Branchadell, Tsuyoshi Kato, Ricardo Rodríguez, Nathalie Saffon-Merceron, Antoine Baceiredo, Thibault Troadec, Morelia Lopez Reyes, Laboratoire Hétérochimie Fondamentale et Appliquée (LHFA), Université Toulouse III - Paul Sabatier (UT3), Université Fédérale Toulouse Midi-Pyrénées-Université Fédérale Toulouse Midi-Pyrénées-Centre National de la Recherche Scientifique (CNRS)-Institut de Chimie du CNRS (INC)-Institut de Chimie de Toulouse (ICT-FR 2599), Institut National Polytechnique (Toulouse) (Toulouse INP), Université Fédérale Toulouse Midi-Pyrénées-Université Fédérale Toulouse Midi-Pyrénées-Centre National de la Recherche Scientifique (CNRS)-Institut de Recherche pour le Développement (IRD)-Université Toulouse III - Paul Sabatier (UT3), Université Fédérale Toulouse Midi-Pyrénées-Institut de Chimie du CNRS (INC)-Institut National Polytechnique (Toulouse) (Toulouse INP), Université Fédérale Toulouse Midi-Pyrénées-Centre National de la Recherche Scientifique (CNRS)-Institut de Recherche pour le Développement (IRD), Institut de Chimie de Toulouse (ICT-FR 2599), Université Fédérale Toulouse Midi-Pyrénées-Institut de Chimie du CNRS (INC), and Universitat Autònoma de Barcelona (UAB)
Subjects: [CHIM.ORGA]Chemical Sciences/Organic chemistry, 010405 organic chemistry, Chemistry, General Chemistry, 010402 general chemistry, Photochemistry, 01 natural sciences, Biochemistry, Catalysis, Cycloaddition, 3. Good health, 0104 chemical sciences, Lewis acid catalysis, Benzaldehyde, chemistry.chemical_compound, Colloid and Surface Chemistry
Abstract: International audience; The synthesis of donor-stabilized silacyclo-butanone 2 was successfully realized by the reaction of silacyclopropylidene 1 with benzaldehyde in the presence of a Lewis acid catalyst. Of particular interest, silacyclobutanone 2 evolves at room temperature via a retro-[2 + 2]-cycloaddition reaction, leading to an original NHC-stabilized 1-silaketene 4 and cis-stilbene.
Published: 2016

31. Carbon Monoxide Activation via O-Bound CO Using Decamethylscandocinium–Hydridoborate Ion Pairs

Author: Odile Eisenstein, Warren E. Piers, Laurent Maron, Ludovic Castro, Andreas Berkefeld, Masood Parvez, Department of Chemistry, University of Calgary, University of Calgary, Laboratoire de physique et chimie des nano-objets (LPCNO), Institut National des Sciences Appliquées - Toulouse (INSA Toulouse), Institut National des Sciences Appliquées (INSA)-Institut National des Sciences Appliquées (INSA)-Institut de Chimie de Toulouse (ICT-FR 2599), Institut National Polytechnique (Toulouse) (Toulouse INP), Université Fédérale Toulouse Midi-Pyrénées-Université Fédérale Toulouse Midi-Pyrénées-Centre National de la Recherche Scientifique (CNRS)-Institut de Recherche pour le Développement (IRD)-Université Toulouse III - Paul Sabatier (UT3), Université Fédérale Toulouse Midi-Pyrénées-Institut de Chimie du CNRS (INC)-Institut National Polytechnique (Toulouse) (Toulouse INP), Université Fédérale Toulouse Midi-Pyrénées-Institut de Chimie du CNRS (INC)-Institut de Recherche sur les Systèmes Atomiques et Moléculaires Complexes (IRSAMC), Institut National des Sciences Appliquées (INSA)-Institut National des Sciences Appliquées (INSA)-Université Toulouse III - Paul Sabatier (UT3), Université Fédérale Toulouse Midi-Pyrénées-Université Fédérale Toulouse Midi-Pyrénées-Centre National de la Recherche Scientifique (CNRS)-Centre National de la Recherche Scientifique (CNRS), Institut Charles Gerhardt Montpellier - Institut de Chimie Moléculaire et des Matériaux de Montpellier (ICGM ICMMM), Ecole Nationale Supérieure de Chimie de Montpellier (ENSCM)-Centre National de la Recherche Scientifique (CNRS)-Université de Montpellier (UM)-Université Montpellier 1 (UM1)-Université Montpellier 2 - Sciences et Techniques (UM2)-Institut de Chimie du CNRS (INC), Institut National des Sciences Appliquées (INSA)-Université de Toulouse (UT)-Institut National des Sciences Appliquées (INSA)-Université de Toulouse (UT)-Institut de Chimie de Toulouse (ICT), Institut de Recherche pour le Développement (IRD)-Université Toulouse III - Paul Sabatier (UT3), Université de Toulouse (UT)-Université de Toulouse (UT)-Institut de Chimie du CNRS (INC)-Centre National de la Recherche Scientifique (CNRS)-Institut National Polytechnique (Toulouse) (Toulouse INP), Université de Toulouse (UT)-Institut de Recherche pour le Développement (IRD)-Université Toulouse III - Paul Sabatier (UT3), Université de Toulouse (UT)-Institut de Chimie du CNRS (INC)-Centre National de la Recherche Scientifique (CNRS)-Institut National Polytechnique (Toulouse) (Toulouse INP), Université de Toulouse (UT)-Institut de Recherche sur les Systèmes Atomiques et Moléculaires Complexes (IRSAMC), Université Toulouse III - Paul Sabatier (UT3), Université de Toulouse (UT)-Université de Toulouse (UT)-Centre National de la Recherche Scientifique (CNRS)-Centre National de la Recherche Scientifique (CNRS), and Université Montpellier 1 (UM1)-Université Montpellier 2 - Sciences et Techniques (UM2)-Ecole Nationale Supérieure de Chimie de Montpellier (ENSCM)-Institut de Chimie du CNRS (INC)-Centre National de la Recherche Scientifique (CNRS)
Subjects: 010405 organic chemistry, Hydride, chemistry.chemical_element, General Chemistry, Borane, 010402 general chemistry, Photochemistry, 01 natural sciences, Biochemistry, Medicinal chemistry, Catalysis, 0104 chemical sciences, Adduct, [CHIM.THEO]Chemical Sciences/Theoretical and/or physical chemistry, chemistry.chemical_compound, Colloid and Surface Chemistry, chemistry, Yield (chemistry), [CHIM.COOR]Chemical Sciences/Coordination chemistry, Scandium, Isomerization, Carbon, Carbon monoxide
Abstract: International audience; Ion pairs [Cp*2Sc]+[HB(p-C6F4R)3]− (R = F, 1-F; R = H, 1-H) were prepared and shown to be unreactive toward D2 and α-olefins, leading to the conclusion that no back-transfer of hydride from boron to scandium occurs. Nevertheless, reaction with CO is observed to yield two products, both ion pairs of the [Cp*2Sc]+ cation with formylborate (2-R) and borataepoxide (3-R) counteranions. DFT calculations show that these products arise from the carbonyl adduct of the [Cp*2Sc]+ in which the CO is bonded to scandium through the oxygen atom, not the carbon atom. The formylborate 2-R is formed in a two-step process initiated by an abstraction of the hydride by the carbon end of an O-bound CO, which forms an η2-formyl intermediate that adds, in a second step, the borane at the carbon. The borataepoxide 3-R is suggested to result from an isomerization of 2-R. This unprecedented reaction represents a new way to activate CO via a reaction channel emanating from the ephemeral isocarbonyl isomer of the CO adduct.
Published: 2012

32. 17O NMR Gives Unprecedented Insights into the Structure of Supported Catalysts and Their Interaction with the Silica Carrier

Author: Marie Genelot, Anne Baudouin, Laurent Maron, Kai Szeto, Nicolas Merle, Régis M. Gauvin, Mostafa Taoufik, André Mortreux, Julien Trébosc, Laurent Delevoye, Iker del Rosal, Laboratoire de Chimie, Catalyse, Polymères et Procédés, R 5265 (C2P2), Université Claude Bernard Lyon 1 (UCBL), Université de Lyon-Université de Lyon-École Supérieure de Chimie Physique Électronique de Lyon (CPE)-Institut de Chimie du CNRS (INC)-Centre National de la Recherche Scientifique (CNRS), Université de Lille, Sciences et Technologies, Laboratoire de physique et chimie des nano-objets (LPCNO), Institut National des Sciences Appliquées - Toulouse (INSA Toulouse), Institut National des Sciences Appliquées (INSA)-Université de Toulouse (UT)-Institut National des Sciences Appliquées (INSA)-Université de Toulouse (UT)-Institut de Chimie de Toulouse (ICT), Institut de Recherche pour le Développement (IRD)-Université Toulouse III - Paul Sabatier (UT3), Université de Toulouse (UT)-Université de Toulouse (UT)-Institut de Chimie du CNRS (INC)-Centre National de la Recherche Scientifique (CNRS)-Institut National Polytechnique (Toulouse) (Toulouse INP), Université de Toulouse (UT)-Institut de Recherche pour le Développement (IRD)-Université Toulouse III - Paul Sabatier (UT3), Université de Toulouse (UT)-Institut de Chimie du CNRS (INC)-Centre National de la Recherche Scientifique (CNRS)-Institut National Polytechnique (Toulouse) (Toulouse INP), Université de Toulouse (UT)-Institut de Recherche sur les Systèmes Atomiques et Moléculaires Complexes (IRSAMC), Université Toulouse III - Paul Sabatier (UT3), Université de Toulouse (UT)-Université de Toulouse (UT)-Centre National de la Recherche Scientifique (CNRS)-Centre National de la Recherche Scientifique (CNRS), Institut de recherches sur la catalyse et l'environnement de Lyon (IRCELYON), Université de Lyon-Université de Lyon-Institut de Chimie du CNRS (INC)-Centre National de la Recherche Scientifique (CNRS), Unité de Catalyse et Chimie du Solide - UMR 8181 (UCCS), Université d'Artois (UA)-Centrale Lille-Institut de Chimie du CNRS (INC)-Université de Lille-Centre National de la Recherche Scientifique (CNRS), Department of Organic Chemistry, Weizmann Institute of Science [Rehovot, Israël], Centre National de la Recherche Scientifique (CNRS)-École supérieure de Chimie Physique Electronique de Lyon (CPE)-Université Claude Bernard Lyon 1 (UCBL), Université de Lyon-Université de Lyon-Institut de Chimie du CNRS (INC), Institut National des Sciences Appliquées (INSA)-Institut National des Sciences Appliquées (INSA)-Institut de Chimie de Toulouse (ICT-FR 2599), Institut National Polytechnique (Toulouse) (Toulouse INP), Université Fédérale Toulouse Midi-Pyrénées-Université Fédérale Toulouse Midi-Pyrénées-Centre National de la Recherche Scientifique (CNRS)-Institut de Recherche pour le Développement (IRD)-Université Toulouse III - Paul Sabatier (UT3), Université Fédérale Toulouse Midi-Pyrénées-Institut de Chimie du CNRS (INC)-Institut National Polytechnique (Toulouse) (Toulouse INP), Université Fédérale Toulouse Midi-Pyrénées-Institut de Chimie du CNRS (INC)-Institut de Recherche sur les Systèmes Atomiques et Moléculaires Complexes (IRSAMC), Institut National des Sciences Appliquées (INSA)-Institut National des Sciences Appliquées (INSA)-Université Toulouse III - Paul Sabatier (UT3), Université Fédérale Toulouse Midi-Pyrénées-Université Fédérale Toulouse Midi-Pyrénées-Centre National de la Recherche Scientifique (CNRS)-Centre National de la Recherche Scientifique (CNRS), Université de Lyon-Université de Lyon-Centre National de la Recherche Scientifique (CNRS)-Institut de Chimie du CNRS (INC), and Centrale Lille Institut (CLIL)-Université d'Artois (UA)-Centrale Lille-Centre National de la Recherche Scientifique (CNRS)-Institut de Chimie du CNRS (INC)-Université de Lille
Subjects: Zirconium, 010405 organic chemistry, Tantalum, Analytical chemistry, chemistry.chemical_element, General Chemistry, [CHIM.INOR]Chemical Sciences/Inorganic chemistry, Tungsten, 010402 general chemistry, 01 natural sciences, Biochemistry, Catalysis, Selective surface, 0104 chemical sciences, Highly sensitive, Colloid and Surface Chemistry, chemistry, Transition metal, [CHIM.ANAL]Chemical Sciences/Analytical chemistry, [CHIM]Chemical Sciences, Local environment, Physical chemistry
Abstract: International audience; Flame silica was surface-labeled with (17)O, through isotopic enrichment of both siloxanes and silanols. After heat treatment at 200 and 700 °C under vacuum, the resulting partially dehydroxylated silica materials were investigated by high-field solid-state (1)H and (17)O NMR. More specifically, MQ MAS and HMQC sequences were used to probe the (17)O local environment. In a further step, these (17)O-tagged supports were used for the preparation of supported catalysts by reaction with perhydrocarbyl transition metal derivatives (zirconium tetraalkyl, tantalum trisalkyl-alkylidene, and tungsten trisalkyl-alkylidyne complexes). Detailed (17)O 1D and 2D MQ and HMQC MAS NMR studies demonstrate that signals in the Si-OH, Si-O-Si, and Si-O-metal regions are highly sensitive to local structural modifications, thanks to (17)O wide chemical shift and quadrupolar constant ranges. Experimental results were supported by DFT calculations. From the selective surface labeling, unprecedented information on interactions between supported catalysts and their inorganic carrier has been extracted.
Published: 2012

33. α-Na3M2(PO4)3 (M = Ti, Fe): Absolute Cationic Ordering in NASICON-Type Phases

Author: Marie Colmont, Houria Kabbour, Christian Masquelier, Daniel Coillot, Olivier Mentré, Unité de Catalyse et Chimie du Solide - UMR 8181 (UCCS), Centrale Lille Institut (CLIL)-Université d'Artois (UA)-Centrale Lille-Centre National de la Recherche Scientifique (CNRS)-Institut de Chimie du CNRS (INC)-Université de Lille, Réseau sur le stockage électrochimique de l'énergie (RS2E), Université de Picardie Jules Verne (UPJV)-Institut de Chimie du CNRS (INC)-Aix Marseille Université (AMU)-Université de Pau et des Pays de l'Adour (UPPA)-Université de Nantes (UN)-Université de Montpellier (UM)-Centre National de la Recherche Scientifique (CNRS)-Sorbonne Université (SU)-Ecole Nationale Supérieure de Chimie de Paris - Chimie ParisTech-PSL (ENSCP), Université Paris sciences et lettres (PSL)-Université Paris sciences et lettres (PSL)-Université de Haute-Alsace (UHA) Mulhouse - Colmar (Université de Haute-Alsace (UHA))-Collège de France (CdF (institution))-Institut polytechnique de Grenoble - Grenoble Institute of Technology (Grenoble INP ), Université Grenoble Alpes (UGA)-Université Grenoble Alpes (UGA)-Institut National Polytechnique (Toulouse) (Toulouse INP), Université Fédérale Toulouse Midi-Pyrénées-Université Fédérale Toulouse Midi-Pyrénées-Ecole Nationale Supérieure de Chimie de Montpellier (ENSCM), Laboratoire réactivité et chimie des solides - UMR CNRS 7314 (LRCS), Université de Picardie Jules Verne (UPJV)-Centre National de la Recherche Scientifique (CNRS)-Institut de Chimie du CNRS (INC), Université d'Artois (UA)-Centrale Lille-Institut de Chimie du CNRS (INC)-Université de Lille-Centre National de la Recherche Scientifique (CNRS), Université de Nantes (UN)-Aix Marseille Université (AMU)-Université de Haute-Alsace (UHA) Mulhouse - Colmar (Université de Haute-Alsace (UHA))-Collège de France (CdF (institution))-Université de Picardie Jules Verne (UPJV)-Ecole Nationale Supérieure de Chimie de Montpellier (ENSCM)-Ecole Nationale Supérieure de Chimie de Paris - Chimie ParisTech-PSL (ENSCP), Université Paris sciences et lettres (PSL)-Université Paris sciences et lettres (PSL)-Université de Pau et des Pays de l'Adour (UPPA)-Institut de Chimie du CNRS (INC)-Université de Montpellier (UM)-Sorbonne Université (SU)-Centre National de la Recherche Scientifique (CNRS)-Institut National Polytechnique (Toulouse) (Toulouse INP), Université de Toulouse (UT)-Université de Toulouse (UT)-Institut polytechnique de Grenoble - Grenoble Institute of Technology (Grenoble INP ), Université Grenoble Alpes (UGA)-Université Grenoble Alpes (UGA), and Université de Picardie Jules Verne (UPJV)-Institut de Chimie du CNRS (INC)-Centre National de la Recherche Scientifique (CNRS)
Subjects: Chemistry, Diffusion, Cationic polymerization, Crystallographic data, [CHIM.MATE]Chemical Sciences/Material chemistry, 02 engineering and technology, General Chemistry, Type (model theory), 010402 general chemistry, 021001 nanoscience & nanotechnology, 01 natural sciences, Biochemistry, Catalysis, 0104 chemical sciences, Crystallography, Colloid and Surface Chemistry, Zigzag, Homogeneous, Vacancy defect, [CHIM.CRIS]Chemical Sciences/Cristallography, Fast ion conductor, 0210 nano-technology
Abstract: International audience; The structure of the fully ordered R-Na3Ti2(PO4)3 NASICON compound was elucidated using highquality single-crystal data. The cation/vacancy distribution forms a homogeneous 3D arrangement and could represent the absolute cationic ordering available in the full Na3M2(PO4)3 series, as verified for M = Fe. For M = Ti, the reversible Rfγ transition was observed at 85 C, leading to the standard disordered R3c γ model. Through JPDF analysis, the most probable Na+ zigzag M(2) M(1) diffusion scheme was directly deduced using our accurate crystallographic data.
Published: 2011

34. Intermediate-Valence Tautomerism in Decamethylytterbocene Complexes of Methyl-Substituted Bipyridines

Author: Richard A. Andersen, Laurent Maron, Marc D. Walter, Daniel Kazhdan, Yung-Jin Hu, Eric D. Bauer, Corwin H. Booth, Evan L. Werkema, Martin Head-Gordon, Wayne W. Lukens, Odile Eisenstein, Lawrence Berkeley National Laboratory [Berkeley] (LBNL), Los Alamos National Laboratory (LANL), Laboratoire de physique et chimie des nano-objets (LPCNO), Institut National des Sciences Appliquées - Toulouse (INSA Toulouse), Institut National des Sciences Appliquées (INSA)-Institut National des Sciences Appliquées (INSA)-Institut de Chimie de Toulouse (ICT-FR 2599), Institut National Polytechnique (Toulouse) (Toulouse INP), Université Fédérale Toulouse Midi-Pyrénées-Université Fédérale Toulouse Midi-Pyrénées-Centre National de la Recherche Scientifique (CNRS)-Institut de Recherche pour le Développement (IRD)-Université Toulouse III - Paul Sabatier (UT3), Université Fédérale Toulouse Midi-Pyrénées-Institut de Chimie du CNRS (INC)-Institut National Polytechnique (Toulouse) (Toulouse INP), Université Fédérale Toulouse Midi-Pyrénées-Institut de Chimie du CNRS (INC)-Institut de Recherche sur les Systèmes Atomiques et Moléculaires Complexes (IRSAMC), Institut National des Sciences Appliquées (INSA)-Institut National des Sciences Appliquées (INSA)-Université Toulouse III - Paul Sabatier (UT3), Université Fédérale Toulouse Midi-Pyrénées-Université Fédérale Toulouse Midi-Pyrénées-Centre National de la Recherche Scientifique (CNRS)-Centre National de la Recherche Scientifique (CNRS), Institut Charles Gerhardt Montpellier - Institut de Chimie Moléculaire et des Matériaux de Montpellier (ICGM ICMMM), Ecole Nationale Supérieure de Chimie de Montpellier (ENSCM)-Centre National de la Recherche Scientifique (CNRS)-Université de Montpellier (UM)-Université Montpellier 1 (UM1)-Université Montpellier 2 - Sciences et Techniques (UM2)-Institut de Chimie du CNRS (INC), Institut National des Sciences Appliquées (INSA)-Université de Toulouse (UT)-Institut National des Sciences Appliquées (INSA)-Université de Toulouse (UT)-Institut de Chimie de Toulouse (ICT), Institut de Recherche pour le Développement (IRD)-Université Toulouse III - Paul Sabatier (UT3), Université de Toulouse (UT)-Université de Toulouse (UT)-Institut de Chimie du CNRS (INC)-Centre National de la Recherche Scientifique (CNRS)-Institut National Polytechnique (Toulouse) (Toulouse INP), Université de Toulouse (UT)-Institut de Recherche pour le Développement (IRD)-Université Toulouse III - Paul Sabatier (UT3), Université de Toulouse (UT)-Institut de Chimie du CNRS (INC)-Centre National de la Recherche Scientifique (CNRS)-Institut National Polytechnique (Toulouse) (Toulouse INP), Université de Toulouse (UT)-Institut de Recherche sur les Systèmes Atomiques et Moléculaires Complexes (IRSAMC), Université Toulouse III - Paul Sabatier (UT3), Université de Toulouse (UT)-Université de Toulouse (UT)-Centre National de la Recherche Scientifique (CNRS)-Centre National de la Recherche Scientifique (CNRS), and Université Montpellier 1 (UM1)-Université Montpellier 2 - Sciences et Techniques (UM2)-Ecole Nationale Supérieure de Chimie de Montpellier (ENSCM)-Institut de Chimie du CNRS (INC)-Centre National de la Recherche Scientifique (CNRS)
Subjects: Valence (chemistry), Extended X-ray absorption fine structure, 010405 organic chemistry, Chemistry, General Chemistry, [CHIM.INOR]Chemical Sciences/Inorganic chemistry, 010402 general chemistry, Photochemistry, 01 natural sciences, Biochemistry, Tautomer, Catalysis, XANES, 0104 chemical sciences, 3. Good health, [CHIM.THEO]Chemical Sciences/Theoretical and/or physical chemistry, Crystallography, Bipyridine, chemistry.chemical_compound, Colloid and Surface Chemistry, Excited state, Singlet state, Ground state
Abstract: International audience; Multiconfigurational, intermediate valent ground states are established in several methyl-substituted bipyridine complexes of bis(pentamethylcyclopentadienyl)ytterbium, Cp2*Yb (Mex-bipy). In contrast to Cp2*Yb(bipy) and other substituted-bipy complexes, the nature of both the ground state and the first excited state are altered by changing the position of the methyl or dimethyl substitutions on the bipyridine rings. In particular, certain substitutions result in multiconfigurational, intermediate valent open-shell singlet states in both the ground state and the first excited state. These conclusions are reached after consideration of single-crystal X-ray diffraction (XRD), the temperature dependence of X-ray absorption near-edge structure (XANES), extended X-ray absorption fine-structure (EXAFS), and magnetic susceptibility data, and are supported by CASSCF-MP2 calculations. These results place the various Cp2*Yb(bipy) complexes in a new tautomeric class, that is, intermediate-valence tautomers.
Published: 2010

35. Decamethylytterbocene Complexes of Bipyridines and Diazabutadienes: Multiconfigurational Ground States and Open-Shell Singlet Formation

Author: Odile Eisenstein, Daniel Kazhdan, Eric D. Bauer, Marc D. Walter, Richard A. Andersen, Laurent Maron, Yung-Jin Hu, Wayne W. Lukens, Corwin H. Booth, Chemical Sciences Division [LBNL Berkeley] (CSD), Lawrence Berkeley National Laboratory [Berkeley] (LBNL), Department of Chemistry [Berkeley], University of California [Berkeley], University of California-University of California, Nuclear Science Division [LBNL Berkeley] (NSD), Materials Physics and Applications Division, Los Alamos National Laboratory (LANL), Laboratoire de physique et chimie des nano-objets (LPCNO), Institut National des Sciences Appliquées - Toulouse (INSA Toulouse), Institut National des Sciences Appliquées (INSA)-Institut National des Sciences Appliquées (INSA)-Institut de Chimie de Toulouse (ICT-FR 2599), Institut National Polytechnique (Toulouse) (Toulouse INP), Université Fédérale Toulouse Midi-Pyrénées-Université Fédérale Toulouse Midi-Pyrénées-Centre National de la Recherche Scientifique (CNRS)-Institut de Recherche pour le Développement (IRD)-Université Toulouse III - Paul Sabatier (UT3), Université Fédérale Toulouse Midi-Pyrénées-Institut de Chimie du CNRS (INC)-Institut National Polytechnique (Toulouse) (Toulouse INP), Université Fédérale Toulouse Midi-Pyrénées-Institut de Chimie du CNRS (INC)-Institut de Recherche sur les Systèmes Atomiques et Moléculaires Complexes (IRSAMC), Institut National des Sciences Appliquées (INSA)-Institut National des Sciences Appliquées (INSA)-Université Toulouse III - Paul Sabatier (UT3), Université Fédérale Toulouse Midi-Pyrénées-Université Fédérale Toulouse Midi-Pyrénées-Centre National de la Recherche Scientifique (CNRS)-Centre National de la Recherche Scientifique (CNRS), Institut Charles Gerhardt Montpellier - Institut de Chimie Moléculaire et des Matériaux de Montpellier (ICGM ICMMM), Ecole Nationale Supérieure de Chimie de Montpellier (ENSCM)-Centre National de la Recherche Scientifique (CNRS)-Université de Montpellier (UM)-Université Montpellier 1 (UM1)-Université Montpellier 2 - Sciences et Techniques (UM2)-Institut de Chimie du CNRS (INC), University of California [Berkeley] (UC Berkeley), University of California (UC)-University of California (UC), Institut National des Sciences Appliquées (INSA)-Université de Toulouse (UT)-Institut National des Sciences Appliquées (INSA)-Université de Toulouse (UT)-Institut de Chimie de Toulouse (ICT), Institut de Recherche pour le Développement (IRD)-Université Toulouse III - Paul Sabatier (UT3), Université de Toulouse (UT)-Université de Toulouse (UT)-Institut de Chimie du CNRS (INC)-Centre National de la Recherche Scientifique (CNRS)-Institut National Polytechnique (Toulouse) (Toulouse INP), Université de Toulouse (UT)-Institut de Recherche pour le Développement (IRD)-Université Toulouse III - Paul Sabatier (UT3), Université de Toulouse (UT)-Institut de Chimie du CNRS (INC)-Centre National de la Recherche Scientifique (CNRS)-Institut National Polytechnique (Toulouse) (Toulouse INP), Université de Toulouse (UT)-Institut de Recherche sur les Systèmes Atomiques et Moléculaires Complexes (IRSAMC), Université Toulouse III - Paul Sabatier (UT3), Université de Toulouse (UT)-Université de Toulouse (UT)-Centre National de la Recherche Scientifique (CNRS)-Centre National de la Recherche Scientifique (CNRS), and Université Montpellier 1 (UM1)-Université Montpellier 2 - Sciences et Techniques (UM2)-Ecole Nationale Supérieure de Chimie de Montpellier (ENSCM)-Institut de Chimie du CNRS (INC)-Centre National de la Recherche Scientifique (CNRS)
Subjects: Valence (chemistry), 010405 organic chemistry, Magnetism, Chemistry, General Chemistry, 010402 general chemistry, 01 natural sciences, Biochemistry, Catalysis, 0104 chemical sciences, Crystallography, Bipyridine, chemistry.chemical_compound, Colloid and Surface Chemistry, Computational chemistry, Density functional theory, [PHYS.PHYS.PHYS-CHEM-PH]Physics [physics]/Physics [physics]/Chemical Physics [physics.chem-ph], Singlet state, Complete active space, Open shell, HOMO/LUMO, ComputingMilieux_MISCELLANEOUS
Abstract: Partial ytterbium f-orbital occupancy (i.e., intermediate valence) and open-shell singlet formation are established for a variety of bipyridine and diazabutadiene adducts with decamethylytterbocene, (C(5)Me(5))(2)Yb, abbreviated as Cp*(2)Yb. Data used to support this claim include ytterbium valence measurements using Yb L(III)-edge X-ray absorption near-edge structure spectroscopy, magnetic susceptibility, and complete active space self-consistent field (CASSCF) multiconfigurational calculations, as well as structural measurements compared to density functional theory calculations. The CASSCF calculations indicate that the intermediate valence is the result of a multiconfigurational ground-state wave function that has both an open-shell singlet f(13)(pi*)(1), where pi* is the lowest unoccupied molecular orbital of the bipyridine or diazabutadiene ligands, and a closed-shell singlet f(14) component. A number of other competing theories for the unusual magnetism in these materials are ruled out by the lack of temperature dependence of the measured intermediate valence. These results have implications for understanding chemical bonding not only in organolanthanide complexes but also for f-element chemistry in general, as well as understanding magnetic interactions in nanoparticles and devices.
Published: 2009

36. Pd(I) Phosphine Carbonyl and Hydride Complexes Implicated in the Palladium-Catalyzed Oxo Process

Author: Nicolaas Meijboom, Lodewijk Schoon, Karina Q. Almeida Leñero, Yohan Champouret, Eite Drent, A. Guy Orpen, Jennifer Houghton, A. Bart van Oort, Jean-Claude Daran, Miguel Baya, Rinaldo Poli, Denes Konya, Wilhelmus P. Mul, Instituto de Ciencia de Materiales de Aragón [Saragoza, España] (ICMA-CSIC), University of Zaragoza - Universidad de Zaragoza [Zaragoza], Laboratoire de chimie de coordination (LCC), Institut de Chimie de Toulouse (ICT), Institut de Recherche pour le Développement (IRD)-Université Toulouse III - Paul Sabatier (UT3), Université de Toulouse (UT)-Université de Toulouse (UT)-Institut de Chimie du CNRS (INC)-Centre National de la Recherche Scientifique (CNRS)-Institut National Polytechnique (Toulouse) (Toulouse INP), Université de Toulouse (UT)-Institut de Recherche pour le Développement (IRD)-Université Toulouse III - Paul Sabatier (UT3), Université de Toulouse (UT)-Centre National de la Recherche Scientifique (CNRS), Shell Global Solutions International B.V., University of Bristol [Bristol], Institut National Polytechnique (Toulouse) (Toulouse INP), Université Fédérale Toulouse Midi-Pyrénées-Université Fédérale Toulouse Midi-Pyrénées-Université Toulouse III - Paul Sabatier (UT3), Université Fédérale Toulouse Midi-Pyrénées-Institut de Chimie de Toulouse (ICT-FR 2599), Université Fédérale Toulouse Midi-Pyrénées-Université Fédérale Toulouse Midi-Pyrénées-Centre National de la Recherche Scientifique (CNRS)-Institut de Recherche pour le Développement (IRD)-Université Toulouse III - Paul Sabatier (UT3), and Université Fédérale Toulouse Midi-Pyrénées-Institut de Chimie du CNRS (INC)-Centre National de la Recherche Scientifique (CNRS)-Institut de Recherche pour le Développement (IRD)-Institut de Chimie du CNRS (INC)-Centre National de la Recherche Scientifique (CNRS)
Subjects: Anions, Stereochemistry, chemistry.chemical_element, Ligands, 010402 general chemistry, 01 natural sciences, Biochemistry, Medicinal chemistry, Redox, Catalysis, Electrolytes, chemistry.chemical_compound, Colloid and Surface Chemistry, Atom, [CHIM.COOR]Chemical Sciences/Coordination chemistry, Redox reactions, 010405 organic chemistry, Hydride, [CHIM.CATA]Chemical Sciences/Catalysis, General Chemistry, 0104 chemical sciences, 3. Good health, [CHIM.THEO]Chemical Sciences/Theoretical and/or physical chemistry, chemistry, Intramolecular force, Palladium, Phosphine, Hydroformylation
Abstract: International audience; Reduction of compound “Pd(bcope)(OTf)2” [bcope = (c-C8H14-1,5)PCH2CH2P(c-C8H14-1,5); OTf = O3SCF3] with H2/CO yields a mixture of Pd(I) compounds [Pd2(bcope)2(CO)2](OTf)2 (1) and [Pd2(bcope)2(μ-CO)(μ-H)](OTf) (2), whereas reduction with H2 or Ph3SiH in the absence of CO leads to [Pd3(bcope)3(μ3-H)2](OTf)2 (3). Exposure of 3 to CO leads to 1 and 2. The structures of 1 and 3 have been determined by X-ray diffraction. Complex [Pd2(bcope)2(CO)2]2+ displays a metal−metal bonded structure with a square planar environment for the Pd atoms and terminally bonded CO ligands and is fluxional in solution. DFT calculations aid the interpretation of this fluxional behavior as resulting from an intramolecular exchange of the two inequivalent P atom positions via a symmetric bis-CO-bridged intermediate. A cyclic voltammetric investigation reveals a very complex redox behavior for the “Pd(bcope)(OTf)2”/CO system and suggests possible pathways leading to the formation of the various observed products, as well as their relationship with the active species of the PdL22+/CO/H2-catalyzed oxo processes (L2 = diphosphine ligands).
Published: 2008

37. Air-persistent monomeric (amino)(carboxy) radicals derived from cyclic (alkyl)(amino) carbenes

Author: Arnold L. Rheingold, Janell K. Mahoney, David C. Martin, Guy Bertrand, Fabrice Thomas, Curtis E. Moore, Département de Chimie Moléculaire - Chimie Inorganique Redox Biomimétique (DCM - CIRE), Département de Chimie Moléculaire (DCM), Université Joseph Fourier - Grenoble 1 (UJF)-Institut de Chimie du CNRS (INC)-Centre National de la Recherche Scientifique (CNRS)-Université Joseph Fourier - Grenoble 1 (UJF)-Institut de Chimie du CNRS (INC)-Centre National de la Recherche Scientifique (CNRS), Laboratoire Hétérochimie Fondamentale et Appliquée (LHFA), Université Toulouse III - Paul Sabatier (UT3), Université Fédérale Toulouse Midi-Pyrénées-Université Fédérale Toulouse Midi-Pyrénées-Centre National de la Recherche Scientifique (CNRS)-Institut de Chimie du CNRS (INC)-Institut de Chimie de Toulouse (ICT-FR 2599), Institut National Polytechnique (Toulouse) (Toulouse INP), Université Fédérale Toulouse Midi-Pyrénées-Université Fédérale Toulouse Midi-Pyrénées-Centre National de la Recherche Scientifique (CNRS)-Institut de Recherche pour le Développement (IRD)-Université Toulouse III - Paul Sabatier (UT3), Université Fédérale Toulouse Midi-Pyrénées-Institut de Chimie du CNRS (INC)-Institut National Polytechnique (Toulouse) (Toulouse INP), and Université Fédérale Toulouse Midi-Pyrénées-Centre National de la Recherche Scientifique (CNRS)-Institut de Recherche pour le Développement (IRD)
Subjects: chemistry.chemical_classification, Trifluoromethyl, 010405 organic chemistry, Radical, Substituent, General Chemistry, 010402 general chemistry, 01 natural sciences, Biochemistry, Peroxide, Endothermic process, Medicinal chemistry, Catalysis, 0104 chemical sciences, chemistry.chemical_compound, Colloid and Surface Chemistry, Monomer, chemistry, Organic chemistry, [CHIM]Chemical Sciences, Alkyl, ComputingMilieux_MISCELLANEOUS
Abstract: A series of monomeric (amino)(carboxy) radicals featuring carbonyl substituents with increasing electron-withdrawing properties (3a, phenyl; 3b, 3,5-bis(trifluoromethyl)phenyl; 3c, perfluorophenyl; 3d, heptafluoropropyl; 3e, 2H-pyrroliumyl) were synthesized in two or three steps from stable cyclic (alky)(amino)carbenes (CAACs). Although (amino)(carboxy) radicals had been previously considered as highly air-sensitive, some of these compounds feature half-lives of hours (3d), and even days (3c and 3e) in well-aerated solutions. DFT calculations show that (amino)(carboxy) radicals evolve from C-centered radical to ambidentate C,O-radicals when increasing the electron-withdrawing properties of the carbonyl substituent. This is paralleled with a destabilization of the peroxide resulting from the addition of dioxygen to the radical. This latter reaction is even predicted to be endothermic for substituents with Hammett constant σp > 0.2.
Published: 2015

38. Iron-catalyzed C-H borylation of arenes

Author: Jean-Baptiste Sortais, C. Gunnar Werncke, Thomas Dombray, Christophe Darcel, Sébastien Bontemps, Mary Grellier, Laure Vendier, Sylviane Sabo-Etienne, Shi Jiang, Institut des Sciences Chimiques de Rennes (ISCR), Centre National de la Recherche Scientifique (CNRS)-Institut de Chimie du CNRS (INC)-Université de Rennes 1 (UR1), Université de Rennes (UNIV-RENNES)-Université de Rennes (UNIV-RENNES)-Ecole Nationale Supérieure de Chimie de Rennes (ENSCR)-Institut National des Sciences Appliquées - Rennes (INSA Rennes), Institut National des Sciences Appliquées (INSA)-Université de Rennes (UNIV-RENNES)-Institut National des Sciences Appliquées (INSA), Laboratoire de chimie de coordination (LCC), Institut National Polytechnique (Toulouse) (Toulouse INP), Université Fédérale Toulouse Midi-Pyrénées-Université Fédérale Toulouse Midi-Pyrénées-Université Toulouse III - Paul Sabatier (UT3), Université Fédérale Toulouse Midi-Pyrénées-Institut de Chimie de Toulouse (ICT-FR 2599), Université Fédérale Toulouse Midi-Pyrénées-Université Fédérale Toulouse Midi-Pyrénées-Centre National de la Recherche Scientifique (CNRS)-Institut de Recherche pour le Développement (IRD)-Université Toulouse III - Paul Sabatier (UT3), Université Fédérale Toulouse Midi-Pyrénées-Institut de Chimie du CNRS (INC)-Centre National de la Recherche Scientifique (CNRS)-Institut de Recherche pour le Développement (IRD)-Institut de Chimie du CNRS (INC)-Centre National de la Recherche Scientifique (CNRS), Université Toulouse III - Paul Sabatier (UT3), Université Fédérale Toulouse Midi-Pyrénées, 12-BS07-0011-01, Agence Nationale de la Recherche, Centre National de la Recherche Scientifique, Université de Rennes (UR)-Institut National des Sciences Appliquées - Rennes (INSA Rennes), Institut National des Sciences Appliquées (INSA)-Institut National des Sciences Appliquées (INSA)-Ecole Nationale Supérieure de Chimie de Rennes (ENSCR)-Institut de Chimie du CNRS (INC)-Centre National de la Recherche Scientifique (CNRS), Institut de Chimie de Toulouse (ICT), Institut de Recherche pour le Développement (IRD)-Université Toulouse III - Paul Sabatier (UT3), Université de Toulouse (UT)-Université de Toulouse (UT)-Institut de Chimie du CNRS (INC)-Centre National de la Recherche Scientifique (CNRS)-Institut National Polytechnique (Toulouse) (Toulouse INP), Université de Toulouse (UT)-Institut de Recherche pour le Développement (IRD)-Université Toulouse III - Paul Sabatier (UT3), Université de Toulouse (UT)-Centre National de la Recherche Scientifique (CNRS), and Université de Toulouse (UT)
Subjects: Borylation, Catalysts, 010405 organic chemistry, Chemistry, Iron catalyzed, Iron, General Chemistry, 010402 general chemistry, 01 natural sciences, Biochemistry, Medicinal chemistry, Catalysis, Hydrocarbons, 0104 chemical sciences, Colloid and Surface Chemistry, Organic chemistry, [CHIM]Chemical Sciences, Reactivity (chemistry), Iron complex, Irradiation, Stoichiometry
Abstract: International audience; Well-defined iron bis(diphosphine) complexes are active catalysts for the dehydrogenative C-H borylation of aromatic and heteroaromatic derivatives with pinacolborane. The corresponding borylated compounds were isolated in moderate to good yields (25-73%) with a 5 mol% catalyst loading under UV irradiation (350 nm) at room temperature. Stoichiometric reactivity studies and isolation of an original trans-hydrido(boryl)iron complex, Fe(H)(Bpin)(dmpe)2, allowed us to propose a mechanism showing the role of some key catalytic species.
Published: 2015

39. Encaging the Verkade’s Superbases: Thermodynamic and Kinetic Consequences

Author: Pascal Dimitrov Raytchev, Jean-Pierre Dutasta, Alexandre Martinez, Heinz Gornitzka, Laboratoire de Chimie - UMR5182 (LC), École normale supérieure de Lyon (ENS de Lyon)-Université Claude Bernard Lyon 1 (UCBL), Université de Lyon-Université de Lyon-Institut de Chimie du CNRS (INC)-Centre National de la Recherche Scientifique (CNRS), Laboratoire de chimie de coordination (LCC), Institut de Chimie de Toulouse (ICT), Institut de Recherche pour le Développement (IRD)-Université Toulouse III - Paul Sabatier (UT3), Université de Toulouse (UT)-Université de Toulouse (UT)-Institut de Chimie du CNRS (INC)-Centre National de la Recherche Scientifique (CNRS)-Institut National Polytechnique (Toulouse) (Toulouse INP), Université de Toulouse (UT)-Institut de Recherche pour le Développement (IRD)-Université Toulouse III - Paul Sabatier (UT3), Université de Toulouse (UT)-Centre National de la Recherche Scientifique (CNRS), Centre National de la Recherche Scientifique (CNRS)-Université Claude Bernard Lyon 1 (UCBL), Université de Lyon-Université de Lyon-École normale supérieure - Lyon (ENS Lyon)-Institut de Chimie du CNRS (INC), Institut National Polytechnique (Toulouse) (Toulouse INP), Université Fédérale Toulouse Midi-Pyrénées-Université Fédérale Toulouse Midi-Pyrénées-Université Toulouse III - Paul Sabatier (UT3), Université Fédérale Toulouse Midi-Pyrénées-Institut de Chimie de Toulouse (ICT-FR 2599), Université Fédérale Toulouse Midi-Pyrénées-Université Fédérale Toulouse Midi-Pyrénées-Centre National de la Recherche Scientifique (CNRS)-Institut de Recherche pour le Développement (IRD)-Université Toulouse III - Paul Sabatier (UT3), and Université Fédérale Toulouse Midi-Pyrénées-Institut de Chimie du CNRS (INC)-Centre National de la Recherche Scientifique (CNRS)-Institut de Recherche pour le Développement (IRD)-Institut de Chimie du CNRS (INC)-Centre National de la Recherche Scientifique (CNRS)
Subjects: Molecular Structure, 010405 organic chemistry, Chemistry, Superbase, Inorganic chemistry, Protonation, General Chemistry, Proazaphosphatrane, Crystallography, X-Ray, 010402 general chemistry, Kinetic energy, 01 natural sciences, Biochemistry, Catalysis, 0104 chemical sciences, [CHIM.THEO]Chemical Sciences/Theoretical and/or physical chemistry, Kinetics, Organophosphorus Compounds, Colloid and Surface Chemistry, Computational chemistry, Thermodynamics, Molecule, Protons
Abstract: International audience; Proazaphosphatranes, also known as Verkade’s superbases, are nonionic species, which exhibit catalytic properties for a wide range of reactions. The properly designed host molecule 3 and its protonated counterpart [3·H]+Cl− were synthesized to study how confinement can modify the stability and the reactivity of a Verkade’s superbase. The results show that the encapsulation does not alter the strong basicity of the proazaphosphatrane, but dramatically decreases the rate of proton transfer.
Published: 2011

40. Activation of aryl halides at gold(I): practical synthesis of (P,C) cyclometalated gold(III) complexes

Author: Didier Bourissou, Johannes Guenther, Sonia Mallet-Ladeira, Laura Estévez, Karinne Miqueu, Abderrahmane Amgoune, Institut des sciences analytiques et de physico-chimie pour l'environnement et les materiaux (IPREM), Centre National de la Recherche Scientifique (CNRS)-Institut de Chimie du CNRS (INC)-Université de Pau et des Pays de l'Adour (UPPA), Laboratoire Hétérochimie Fondamentale et Appliquée (LHFA), Université Toulouse III - Paul Sabatier (UT3), Université Fédérale Toulouse Midi-Pyrénées-Université Fédérale Toulouse Midi-Pyrénées-Centre National de la Recherche Scientifique (CNRS)-Institut de Chimie du CNRS (INC)-Institut de Chimie de Toulouse (ICT-FR 2599), Institut National Polytechnique (Toulouse) (Toulouse INP), Université Fédérale Toulouse Midi-Pyrénées-Université Fédérale Toulouse Midi-Pyrénées-Centre National de la Recherche Scientifique (CNRS)-Institut de Recherche pour le Développement (IRD)-Université Toulouse III - Paul Sabatier (UT3), Université Fédérale Toulouse Midi-Pyrénées-Institut de Chimie du CNRS (INC)-Institut National Polytechnique (Toulouse) (Toulouse INP), and Université Fédérale Toulouse Midi-Pyrénées-Centre National de la Recherche Scientifique (CNRS)-Institut de Recherche pour le Développement (IRD)
Subjects: Chemistry, Aryl, Halide, General Chemistry, Photochemistry, Biochemistry, Medicinal chemistry, Oxidative addition, Catalysis, chemistry.chemical_compound, Colloid and Surface Chemistry, Gold iii, Atom, [CHIM]Chemical Sciences, Chelation, Phosphine
Abstract: International audience; Taking advantage of phosphine chelation, direct evidence for oxidative addition of Csp2-X bonds (X = I, Br) to a single gold atom is reported. NMR studies and DFT calculations provide insight into this unprecedented transformation, which gives straightforward access to stable (P,C) cyclometalated gold(III) complexes. © 2014 American Chemical Society.
Published: 2014

41. 1-arsa-3-germaallene Tip(t-Bu)Ge═C═AsMes*: the heaviest mixed group 14 and 15 heteroallenic compound

Author: Jean-Marc Sotiropoulos, Karinne Miqueu, Jean Escudié, Dumitru Ghereg, Nathalie Saffon, Laboratoire Hétérochimie Fondamentale et Appliquée (LHFA), Université Toulouse III - Paul Sabatier (UT3), Université Fédérale Toulouse Midi-Pyrénées-Université Fédérale Toulouse Midi-Pyrénées-Centre National de la Recherche Scientifique (CNRS)-Institut de Chimie du CNRS (INC)-Institut de Chimie de Toulouse (ICT-FR 2599), Institut National Polytechnique (Toulouse) (Toulouse INP), Université Fédérale Toulouse Midi-Pyrénées-Université Fédérale Toulouse Midi-Pyrénées-Centre National de la Recherche Scientifique (CNRS)-Institut de Recherche pour le Développement (IRD)-Université Toulouse III - Paul Sabatier (UT3), Université Fédérale Toulouse Midi-Pyrénées-Institut de Chimie du CNRS (INC)-Institut National Polytechnique (Toulouse) (Toulouse INP), Université Fédérale Toulouse Midi-Pyrénées-Centre National de la Recherche Scientifique (CNRS)-Institut de Recherche pour le Développement (IRD), Structure Fédérative Toulousaine en Chimie Moléculaire (SFTCM), Université Fédérale Toulouse Midi-Pyrénées-Université Fédérale Toulouse Midi-Pyrénées-Université Toulouse III - Paul Sabatier (UT3), Université Fédérale Toulouse Midi-Pyrénées-Centre National de la Recherche Scientifique (CNRS), Institut des sciences analytiques et de physico-chimie pour l'environnement et les materiaux (IPREM), Centre National de la Recherche Scientifique (CNRS)-Institut de Chimie du CNRS (INC)-Université de Pau et des Pays de l'Adour (UPPA), Institut Pluridisciplinaire de Recherche sur l'Environnement et les Matériaux (IPREM), and Université de Pau et des Pays de l'Adour (UPPA)-Centre National de la Recherche Scientifique (CNRS)
Subjects: Models, Molecular, Double bond, Stereochemistry, 010402 general chemistry, Crystallography, X-Ray, 01 natural sciences, Biochemistry, Catalysis, Arsenic, chemistry.chemical_compound, Colloid and Surface Chemistry, Group (periodic table), Organometallic Compounds, Mixed group, [CHIM.COOR]Chemical Sciences/Coordination chemistry, Chemoselectivity, Electronic properties, chemistry.chemical_classification, Molecular Structure, 010405 organic chemistry, Chemistry, [CHIM.ORGA]Chemical Sciences/Organic chemistry, Germanium, Stereoisomerism, General Chemistry, [CHIM.CATA]Chemical Sciences/Catalysis, Dimethylbutadiene, 0104 chemical sciences, [CHIM.THEO]Chemical Sciences/Theoretical and/or physical chemistry, Crystallography, [CHIM.POLY]Chemical Sciences/Polymers, Quantum Theory, Methanol
Abstract: cited By 8; International audience; The 1-arsa-3-germaallene Tip(t-Bu)Ge=C=AsMes* (1, Tip = 2,4,6-triisopropylphenyl, Mes* = 2,4,6-tri-tert-butylphenyl), a stable heavier group 14 and 15 congener of allenes, has been synthesized by debromofluorination of Tip(t-Bu)Ge(F)-C(Br)=AsMes. It reacts with methanol and 2,3-dimethyl-1,3-butadiene by the Ge=C double bond. The allenic-type structure of 1, featuring cumulated Ge=C and C=As double bonds, has been evidenced by means of spectroscopic and single-crystal X-ray determination. The electronic properties involved in this new system were obtained from DFT calculations. The mechanism of the reaction between 1 and the dimethylbutadiene is also described to understand the observed regio- and chemoselectivity. © 2011 American Chemical Society.
Published: 2011

42. Hydrido-ruthenium cluster complexes as models for reactive surface hydrogen species of ruthenium nanoparticles. Solid-state 2H NMR and quantum chemical calculations

Author: Xu Yeping, Guy Lavigne, Rosa Axet, Iker del Rosal, Torsten Gutmann, Maria Wächtler, Bernadeta Walaszek, Hans-Heinrich Limbach, Bruno Chaudret, Gerd Buntkowsky, Romuald Poteau, Anna Grünberg, Institute of Physical Chemistry, Darmstadt University of Technology [Darmstadt], Laboratoire de physique et chimie des nano-objets (LPCNO), Institut National des Sciences Appliquées - Toulouse (INSA Toulouse), Institut National des Sciences Appliquées (INSA)-Université de Toulouse (UT)-Institut National des Sciences Appliquées (INSA)-Université de Toulouse (UT)-Institut de Chimie de Toulouse (ICT), Institut de Recherche pour le Développement (IRD)-Université Toulouse III - Paul Sabatier (UT3), Université de Toulouse (UT)-Université de Toulouse (UT)-Institut de Chimie du CNRS (INC)-Centre National de la Recherche Scientifique (CNRS)-Institut National Polytechnique (Toulouse) (Toulouse INP), Université de Toulouse (UT)-Institut de Recherche pour le Développement (IRD)-Université Toulouse III - Paul Sabatier (UT3), Université de Toulouse (UT)-Institut de Chimie du CNRS (INC)-Centre National de la Recherche Scientifique (CNRS)-Institut National Polytechnique (Toulouse) (Toulouse INP), Université de Toulouse (UT)-Institut de Recherche sur les Systèmes Atomiques et Moléculaires Complexes (IRSAMC), Université Toulouse III - Paul Sabatier (UT3), Université de Toulouse (UT)-Université de Toulouse (UT)-Centre National de la Recherche Scientifique (CNRS)-Centre National de la Recherche Scientifique (CNRS), Laboratoire de chimie de coordination (LCC), Institut de Chimie de Toulouse (ICT), Université de Toulouse (UT)-Centre National de la Recherche Scientifique (CNRS), Institut für Chemie und Biochemie [Berlin], Freie Universität Berlin, Institut National des Sciences Appliquées (INSA)-Institut National des Sciences Appliquées (INSA)-Institut de Chimie de Toulouse (ICT-FR 2599), Institut National Polytechnique (Toulouse) (Toulouse INP), Université Fédérale Toulouse Midi-Pyrénées-Université Fédérale Toulouse Midi-Pyrénées-Centre National de la Recherche Scientifique (CNRS)-Institut de Recherche pour le Développement (IRD)-Université Toulouse III - Paul Sabatier (UT3), Université Fédérale Toulouse Midi-Pyrénées-Institut de Chimie du CNRS (INC)-Institut National Polytechnique (Toulouse) (Toulouse INP), Université Fédérale Toulouse Midi-Pyrénées-Institut de Chimie du CNRS (INC)-Institut de Recherche sur les Systèmes Atomiques et Moléculaires Complexes (IRSAMC), Institut National des Sciences Appliquées (INSA)-Institut National des Sciences Appliquées (INSA)-Université Toulouse III - Paul Sabatier (UT3), Université Fédérale Toulouse Midi-Pyrénées-Université Fédérale Toulouse Midi-Pyrénées-Centre National de la Recherche Scientifique (CNRS)-Centre National de la Recherche Scientifique (CNRS), Université Fédérale Toulouse Midi-Pyrénées-Université Fédérale Toulouse Midi-Pyrénées-Université Toulouse III - Paul Sabatier (UT3), Université Fédérale Toulouse Midi-Pyrénées-Institut de Chimie de Toulouse (ICT-FR 2599), and Université Fédérale Toulouse Midi-Pyrénées-Institut de Chimie du CNRS (INC)-Centre National de la Recherche Scientifique (CNRS)-Institut de Recherche pour le Développement (IRD)-Institut de Chimie du CNRS (INC)-Centre National de la Recherche Scientifique (CNRS)
Subjects: Magnetic Resonance Spectroscopy, Hydrogen, Surface Properties, Solid-state, chemistry.chemical_element, Nanoparticle, Metal Nanoparticles, Molecular Dynamics Simulation, 010402 general chemistry, 01 natural sciences, Biochemistry, Catalysis, Ruthenium, Colloid and Surface Chemistry, Computational chemistry, Cluster (physics), Organometallic Compounds, [CHIM]Chemical Sciences, [CHIM.COOR]Chemical Sciences/Coordination chemistry, ComputingMilieux_MISCELLANEOUS, Quantum chemical, 010405 organic chemistry, General Chemistry, [CHIM.CATA]Chemical Sciences/Catalysis, [CHIM.MATE]Chemical Sciences/Material chemistry, 0104 chemical sciences, Characterization (materials science), chemistry, Quantum Theory
Abstract: The (2)H quadrupolar interaction is a sensitive tool for the characterization of deuterium-metal binding states. In the present study, experimental solid-state (2)H MAS NMR techniques are used in the investigations of two ruthenium clusters, D(4)Ru(4)(CO)(12) (1) and D(2)Ru(6)(CO)(18) (2), which serve as model compounds for typical two-fold, three-fold, and octahedral coordination sites on metal surfaces. By line-shape analysis of the (2)H MAS NMR measurements of sample 1, a quadrupolar coupling constant of 67 +/- 1 kHz, an asymmetry parameter of 0.67 +/- 0.1, and an isotropic chemical shift of -17.4 ppm are obtained. In addition to the neutral complex, sample 2 includes two ionic clusters, identified as anionic [DRu(6)(CO)(18)](-) (2(-)) and cationic [D(3)Ru(6)(CO)(18)](+) (2(+)). By virtue of the very weak quadrupolar interaction (2 kHz) and the strong low-field shift (+16.8 ppm) of 2(-), it is shown that the deuteron is located in the symmetry center of the octahedron spanned by the six ruthenium atoms. For the cationic 2(+), the quadrupolar interaction is similar to that of the neutral 2. Quantum chemical DFT calculations at different model structures for these ruthenium clusters were arranged in order to help in the interpretation of the experimental results. It is shown that the (2)H nuclear quadrupolar interaction is a sensitive tool for distinguishing the binding state of the deuterons to the transition metal. Combining the data from the polynuclear complexes with the data from mononuclear complexes, a molecular ruler for quadrupolar interactions is created. This ruler now permits the solid-state NMR spectroscopic characterization of deuterium adsorbed on the surfaces of catalytically active metal nanoparticles.
Published: 2010

43. Fluoride ion chelation by a bidentate phosphonium/borane Lewis acid

Author: Todd W. Hudnall, Young-Min Kim, Didier Bourissou, Magnus William Paul Bebbington, François P. Gabbaï, Laboratoire Hétérochimie Fondamentale et Appliquée (LHFA), Université Toulouse III - Paul Sabatier (UT3), Université Fédérale Toulouse Midi-Pyrénées-Université Fédérale Toulouse Midi-Pyrénées-Centre National de la Recherche Scientifique (CNRS)-Institut de Chimie du CNRS (INC)-Institut de Chimie de Toulouse (ICT-FR 2599), Institut National Polytechnique (Toulouse) (Toulouse INP), Université Fédérale Toulouse Midi-Pyrénées-Université Fédérale Toulouse Midi-Pyrénées-Centre National de la Recherche Scientifique (CNRS)-Institut de Recherche pour le Développement (IRD)-Université Toulouse III - Paul Sabatier (UT3), Université Fédérale Toulouse Midi-Pyrénées-Institut de Chimie du CNRS (INC)-Institut National Polytechnique (Toulouse) (Toulouse INP), Université Fédérale Toulouse Midi-Pyrénées-Centre National de la Recherche Scientifique (CNRS)-Institut de Recherche pour le Développement (IRD), Department of Chemistry, and Texas A&M University [College Station]
Subjects: Models, Molecular, Inorganic chemistry, Borane, Alkylation, 010402 general chemistry, Crystallography, X-Ray, 01 natural sciences, Biochemistry, Medicinal chemistry, Catalysis, chemistry.chemical_compound, Fluorides, Colloid and Surface Chemistry, Organophosphorus Compounds, Moiety, Chelation, Lewis acids and bases, Phosphonium, Boranes, ComputingMilieux_MISCELLANEOUS, Chelating Agents, Ions, Molecular Structure, 010405 organic chemistry, [CHIM.ORGA]Chemical Sciences/Organic chemistry, General Chemistry, Binding constant, 3. Good health, 0104 chemical sciences, chemistry, Models, Chemical, Fluoride, Acids
Abstract: The phosphonium borane [1-Mes2B-2-MePh2P-(C6H4)]+ ([2]+) has been synthesized as an iodide salt by alkylation of 1-Mes2B-2-Ph2P-(C6H4) with MeI. This novel cationic borane complexes fluoride to afford the corresponding zwitterionic fluoroborate complex 1-FMes2B-2-MePh2P-(C6H4) (2-F) with a binding constant in MeOH exceeding that of 1-Mes2B-4-MePh2P-(C6H4) ([1]+) by at least 4 orders of magnitude. Structural and computational results indicate that the high fluorophilicity of [2]+ arises from both Coulombic and cooperative effects which lead to formation of a B-F--P interaction with a F--P distance of 2.666(2) A. These results, which are supported by NBO and AIM analyses, show that the latent phosphorus-centered Lewis acidity of the phosphonium moiety in [2]+ can be exploited to enhance fluoride binding via chelation.
Published: 2008

44. Electronic and magnetic communication in mixed-valent and homovalent ruthenium complexes containing phenylcyanamide type bridging ligands

Author: Muriel Fabre, Jacques Bonvoisin, Groupe NanoSciences (CEMES-GNS), Centre d'élaboration de matériaux et d'études structurales (CEMES), Université Toulouse III - Paul Sabatier (UT3), Université Fédérale Toulouse Midi-Pyrénées-Université Fédérale Toulouse Midi-Pyrénées-Centre National de la Recherche Scientifique (CNRS)-Institut de Chimie de Toulouse (ICT-FR 2599), Institut National Polytechnique (Toulouse) (Toulouse INP), Université Fédérale Toulouse Midi-Pyrénées-Université Fédérale Toulouse Midi-Pyrénées-Centre National de la Recherche Scientifique (CNRS)-Institut de Recherche pour le Développement (IRD)-Université Toulouse III - Paul Sabatier (UT3), Université Fédérale Toulouse Midi-Pyrénées-Institut de Chimie du CNRS (INC)-Institut National Polytechnique (Toulouse) (Toulouse INP), Université Fédérale Toulouse Midi-Pyrénées-Centre National de la Recherche Scientifique (CNRS)-Institut de Recherche pour le Développement (IRD)-Institut de Chimie du CNRS (INC)-Institut National des Sciences Appliquées - Toulouse (INSA Toulouse), Institut National des Sciences Appliquées (INSA)-Institut National des Sciences Appliquées (INSA)-Université Toulouse III - Paul Sabatier (UT3), Institut National des Sciences Appliquées (INSA)-Institut National des Sciences Appliquées (INSA), Institut National des Sciences Appliquées - Toulouse (INSA Toulouse), Institut National des Sciences Appliquées (INSA)-Université de Toulouse (UT)-Institut National des Sciences Appliquées (INSA)-Université de Toulouse (UT)-Institut de Chimie de Toulouse (ICT), Institut de Recherche pour le Développement (IRD)-Université Toulouse III - Paul Sabatier (UT3), Université de Toulouse (UT)-Université de Toulouse (UT)-Institut de Chimie du CNRS (INC)-Centre National de la Recherche Scientifique (CNRS)-Institut National Polytechnique (Toulouse) (Toulouse INP), Université de Toulouse (UT)-Institut de Recherche pour le Développement (IRD)-Université Toulouse III - Paul Sabatier (UT3), Université de Toulouse (UT)-Institut de Chimie du CNRS (INC)-Centre National de la Recherche Scientifique (CNRS)-Institut National Polytechnique (Toulouse) (Toulouse INP), Université de Toulouse (UT)-Centre National de la Recherche Scientifique (CNRS)-Institut National des Sciences Appliquées - Toulouse (INSA Toulouse), and Université de Toulouse (UT)-Centre National de la Recherche Scientifique (CNRS)
Subjects: spectroscopy, Inorganic chemistry, cyanamide, Intermetallic, Electron-transfer, chemistry.chemical_element, 010402 general chemistry, 01 natural sciences, Biochemistry, Catalysis, Ruthenium, law.invention, chemistry.chemical_compound, Paramagnetism, Colloid and Surface Chemistry, law, Mixed-valence, [CHIM.COOR]Chemical Sciences/Coordination chemistry, Electron paramagnetic resonance, Spectroelectrochemistry, dinuclear complex, Anthracene, Exchange interaction, complexes, Diacetylene, 010405 organic chemistry, General Chemistry, Inductive coupling, 3. Good health, 0104 chemical sciences, Magnetic coupling, Crystallography, chemistry, Acetylene, Electrochemical properties, EPR
Abstract: International audience; Four new phenylcyanamido-bridge dinuclear ruthenium complexes [{Ru(tpy)(thd)}2(μ-L)] with tpy = 2,2‘:6‘,2‘ ‘-terpyridine, thd = 2,2,6,6-tetramethyl-3,5-heptanedione and L = dcbp = 4,4‘-dicyanamidobiphenyl; bcpa = bis(4-cyanamidophenyl)acetylene; bcpda = bis(4-cyanamidophenyl)diacetylene; bcpea = 9,10,-bis(4-cyanamidophenylethynyl)anthracene have been prepared and fully characterized. The mixed valent Ru(II)Ru(III) and homovalent paramagnetic Ru(III)Ru(III) forms of all the complexes were electrochemically generated and studied by UV−vis−NIR and EPR spectroscopy. Electronic communication was quantified by the electronic coupling parameter Vab extracted from intervalence measurements in the near IR area, and magnetic communication was quantified in terms of the exchange coupling constant J, accessible from the intensity of the EPR signal when varying the temperature. Exponential decays for both electronic and magnetic coupling versus intermetallic distance were obtained and discussed.
Published: 2007

45. An activated equivalent of lactide toward organocatalytic ring-opening polymerization

Author: † Blanca Martin-Vaca, Olivier Thillaye du Boullay, Didier Bourissou, Emmanuel Marchal, and Fernando P. Cossío, Laboratoire Hétérochimie Fondamentale et Appliquée (LHFA), Université Toulouse III - Paul Sabatier (UT3), Université Fédérale Toulouse Midi-Pyrénées-Université Fédérale Toulouse Midi-Pyrénées-Centre National de la Recherche Scientifique (CNRS)-Institut de Chimie du CNRS (INC)-Institut de Chimie de Toulouse (ICT-FR 2599), Institut National Polytechnique (Toulouse) (Toulouse INP), Université Fédérale Toulouse Midi-Pyrénées-Université Fédérale Toulouse Midi-Pyrénées-Centre National de la Recherche Scientifique (CNRS)-Institut de Recherche pour le Développement (IRD)-Université Toulouse III - Paul Sabatier (UT3), Université Fédérale Toulouse Midi-Pyrénées-Institut de Chimie du CNRS (INC)-Institut National Polytechnique (Toulouse) (Toulouse INP), Université Fédérale Toulouse Midi-Pyrénées-Centre National de la Recherche Scientifique (CNRS)-Institut de Recherche pour le Développement (IRD), DEPARTAMENTO DE QUIMICA ORGANICA I/KIMIKA, and Universidad del Pais Vasco / Euskal Herriko Unibertsitatea [Espagne] (UPV/EHU)
Subjects: Polymers, Polyesters, Molecular Conformation, Stereoisomerism, 010402 general chemistry, 01 natural sciences, Biochemistry, Ring-opening polymerization, Molecular conformation, Catalysis, chemistry.chemical_compound, Colloid and Surface Chemistry, Polymer chemistry, Organic chemistry, Reactivity (chemistry), Lactic Acid, ComputingMilieux_MISCELLANEOUS, chemistry.chemical_classification, Lactide, 010405 organic chemistry, [CHIM.ORGA]Chemical Sciences/Organic chemistry, General Chemistry, 3. Good health, 0104 chemical sciences, Polyester, chemistry, Lactone
Abstract: The alpha-lactone equivalent lacOCA exhibits remarkable reactivity compared with lactide in nucleophile-catalyzed ROP. PLAs of controlled molecular weights and narrow polydispersities are typically obtained under mild conditions using DMAP and various protic initiators.
Published: 2006

46. Octasubstituted metal-free phthalocyanine as core of phosphorus dendrimers: a probe for the properties of the internal structure

Author: Julien Leclaire, Rodolphe Dagiral, Jean-Pierre Majoral, Yannick Coppel, Suzanne Fery-Forgues, Bruno Donnadieu, Anne-Marie Caminade, Interactions moléculaires et réactivité chimique et photochimique (IMRCP), Université Toulouse III - Paul Sabatier (UT3), Université Fédérale Toulouse Midi-Pyrénées-Université Fédérale Toulouse Midi-Pyrénées-Centre National de la Recherche Scientifique (CNRS)-Institut de Chimie du CNRS (INC)-Institut de Chimie de Toulouse (ICT-FR 2599), Institut de Recherche pour le Développement (IRD)-Université Toulouse III - Paul Sabatier (UT3), Université Fédérale Toulouse Midi-Pyrénées-Université Fédérale Toulouse Midi-Pyrénées-Institut de Chimie du CNRS (INC)-Centre National de la Recherche Scientifique (CNRS)-Institut National Polytechnique (Toulouse) (Toulouse INP), Université Fédérale Toulouse Midi-Pyrénées-Institut de Recherche pour le Développement (IRD)-Centre National de la Recherche Scientifique (CNRS)-Institut National Polytechnique (Toulouse) (Toulouse INP), Université Fédérale Toulouse Midi-Pyrénées, Institut de Chimie de Toulouse (ICT), Université de Toulouse (UT)-Université de Toulouse (UT)-Institut de Chimie du CNRS (INC)-Centre National de la Recherche Scientifique (CNRS)-Institut National Polytechnique (Toulouse) (Toulouse INP), Université de Toulouse (UT)-Institut de Recherche pour le Développement (IRD)-Université Toulouse III - Paul Sabatier (UT3), Université de Toulouse (UT)-Institut Ecologie et Environnement (INEE), Centre National de la Recherche Scientifique (CNRS)-Centre National de la Recherche Scientifique (CNRS)-Fédération de Recherche Fluides, Energie, Réacteurs, Matériaux et Transferts (FERMAT), Institut National des Sciences Appliquées - Toulouse (INSA Toulouse), Institut National des Sciences Appliquées (INSA)-Université de Toulouse (UT)-Institut National des Sciences Appliquées (INSA)-Université de Toulouse (UT)-Université Toulouse III - Paul Sabatier (UT3), Université de Toulouse (UT)-Centre National de la Recherche Scientifique (CNRS)-Institut National Polytechnique (Toulouse) (Toulouse INP), Université de Toulouse (UT)-Institut National des Sciences Appliquées - Toulouse (INSA Toulouse), Institut National des Sciences Appliquées (INSA)-Université de Toulouse (UT)-Institut National des Sciences Appliquées (INSA)-Centre National de la Recherche Scientifique (CNRS)-Centre National de la Recherche Scientifique (CNRS), and Horace, Josiane
Subjects: Aqueous solution, 010405 organic chemistry, Fluorescence spectrometry, Analytical chemistry, Quantum yield, General Chemistry, Chromophore, 010402 general chemistry, Photochemistry, 01 natural sciences, Biochemistry, Catalysis, 0104 chemical sciences, Solvent, chemistry.chemical_compound, Colloid and Surface Chemistry, chemistry, Dendrimer, Bathochromic shift, Phthalocyanine
Abstract: The synthesis of a new family of phosphorus dendrimers built from an octasubstituted metal-free phthalocyanine core is described up to generation 5. This core is used as a sensor and a probe for analyzing the properties of the internal structure and the influence of each structural part (core, branches, surface) upon the whole structure. UV-visible spectra show both a hyperchromic and bathochromic effect on the Q-bands with increasing generation, indicating that the chromophore is more isolated, and that the dendritic shell mimics a highly polar solvent. There is no evidence for aggregation, except for generation 0, showing again the isolation of the core. However, the dendritic shell is permeable to aqueous acids and bases, as demonstrated by the reversible splitting of the Q-band in an acidic medium (neutral form of the phthalocyanine) and the single Q-band in a basic medium (dianionic form), even for generation 4. The fluorescence quantum yield for the neutral form increases with increasing generation. The dianionic form of generation 0 is poorly fluorescent, whereas generations 3 and 4 (G3 and G4) exhibit better fluorescence. The cores of G3 and G4 are highly sensitive optical sensors for H3O+ and OH-. These experiments are carried out in THF/water mixtures, and the influence of water on the structure has been checked. The hydrodynamic radius of generation 4 is measured by NMR diffusion (pulse gradient spin-echo) experiments. R(H) varies from 35.4 A at 4 mol % of water to 32.5 A at 64 mol % of water in THF, indicating the hydrophobic nature of these dendrimers.
Published: 2005

47. Evidence for radical fragmentations from persistent singlet carbenes

Author: Xavier Cattoën, Didier Bourissou, Karinne Miqueu, Guy Bertrand, Heinz Gornitzka, AM2N, Department of Chemistry [Riverside], University of California [Riverside] (UCR), University of California-University of California-University of California [Riverside] (UCR), University of California-University of California, LABORATOIRE DE CHIMIE THEORIQUE ET PHYSICO-CHIMIE MOLECULAIRE (LCTPCM), Université de Pau et des Pays de l'Adour (UPPA)-Centre National de la Recherche Scientifique (CNRS), Laboratoire Hétérochimie Fondamentale et Appliquée (LHFA), Université Toulouse III - Paul Sabatier (UT3), Université Fédérale Toulouse Midi-Pyrénées-Université Fédérale Toulouse Midi-Pyrénées-Centre National de la Recherche Scientifique (CNRS)-Institut de Chimie du CNRS (INC)-Institut de Chimie de Toulouse (ICT-FR 2599), Institut National Polytechnique (Toulouse) (Toulouse INP), Université Fédérale Toulouse Midi-Pyrénées-Université Fédérale Toulouse Midi-Pyrénées-Centre National de la Recherche Scientifique (CNRS)-Institut de Recherche pour le Développement (IRD)-Université Toulouse III - Paul Sabatier (UT3), Université Fédérale Toulouse Midi-Pyrénées-Institut de Chimie du CNRS (INC)-Institut National Polytechnique (Toulouse) (Toulouse INP), and Université Fédérale Toulouse Midi-Pyrénées-Centre National de la Recherche Scientifique (CNRS)-Institut de Recherche pour le Développement (IRD)
Subjects: 010405 organic chemistry, Stereochemistry, [CHIM.ORGA]Chemical Sciences/Organic chemistry, General Chemistry, 010402 general chemistry, Photochemistry, 01 natural sciences, Biochemistry, Catalysis, 0104 chemical sciences, Homolysis, chemistry.chemical_compound, Colloid and Surface Chemistry, chemistry, Fragmentation (mass spectrometry), Singlet state, Carbene, ComputingMilieux_MISCELLANEOUS
Abstract: Upon warm up, persistent aminohydrazinocarbenes undergo beta-fragmentation reactions. Experimental as well as computational evidences are reported for the involvement of radical processes. This is the first example of a homolytic fragmentation for a persistent singlet carbene.
Published: 2005

48. Under Pressure: Mechanochemical Effects on Structure and Ion Conduction in the Sodium-Ion Solid Electrolyte Na3PS4

Author: O. Ulas Kudu, Wolfgang G. Zeier, Olaf J. Borkiewicz, Emmanuelle Suard, M. Saiful Islam, Christian Masquelier, Steffen P. Emge, Pieremanuele Canepa, Houssny Bouyanfif, James A. Dawson, Mohamed Zbiri, Theodosios Famprikis, François Fauth, Clare P. Grey, Damien Dambournet, Jean-Noël Chotard, Sorina Cretu, University of Cambridge [UK] (CAM), Physikalisch-Chemisches Institut, Justus-Liebig-Universität Gießen = Justus Liebig University (JLU), University of Bath [Bath], Advanced Lithium Energy Storage Systems - ALISTORE-ERI (ALISTORE-ERI), Institut de Chimie du CNRS (INC)-Centre National de la Recherche Scientifique (CNRS), Laboratoire réactivité et chimie des solides - UMR CNRS 7314 (LRCS), Université de Picardie Jules Verne (UPJV)-Institut de Chimie du CNRS (INC)-Centre National de la Recherche Scientifique (CNRS), Réseau sur le stockage électrochimique de l'énergie (RS2E), Université de Nantes (UN)-Aix Marseille Université (AMU)-Université de Haute-Alsace (UHA) Mulhouse - Colmar (Université de Haute-Alsace (UHA))-Collège de France (CdF (institution))-Université de Picardie Jules Verne (UPJV)-Ecole Nationale Supérieure de Chimie de Montpellier (ENSCM)-Ecole Nationale Supérieure de Chimie de Paris - Chimie ParisTech-PSL (ENSCP), Université Paris sciences et lettres (PSL)-Université Paris sciences et lettres (PSL)-Université de Pau et des Pays de l'Adour (UPPA)-Institut de Chimie du CNRS (INC)-Université de Montpellier (UM)-Sorbonne Université (SU)-Centre National de la Recherche Scientifique (CNRS)-Institut National Polytechnique (Toulouse) (Toulouse INP), Université de Toulouse (UT)-Université de Toulouse (UT)-Institut polytechnique de Grenoble - Grenoble Institute of Technology (Grenoble INP ), Université Grenoble Alpes (UGA)-Université Grenoble Alpes (UGA), Delft University of Technology (TU Delft), National University of Singapore (NUS), CELLS ALBA, Barcelona 08290, Spain, Institut Laue-Langevin (ILL), PHysicochimie des Electrolytes et Nanosystèmes InterfaciauX (PHENIX), Institut de Chimie du CNRS (INC)-Sorbonne Université (SU)-Centre National de la Recherche Scientifique (CNRS), X-ray Science Division (XSD), Laboratoire de Physique de la Matière Condensée - UR UPJV 2081 (LPMC), and Université de Picardie Jules Verne (UPJV)
Subjects: Materials science, Chemistry(all), Ab initio, Thermodynamics, Electrolyte, 010402 general chemistry, 01 natural sciences, Biochemistry, Catalysis, Ion, Tetragonal crystal system, symbols.namesake, Colloid and Surface Chemistry, Fast ion conductor, Ionic conductivity, Ceramic, Chemistry, Pair distribution function, [CHIM.MATE]Chemical Sciences/Material chemistry, General Chemistry, 0104 chemical sciences, Dielectric spectroscopy, visual_art, visual_art.visual_art_medium, symbols, Raman spectroscopy
Abstract: Fast-ion conductors are critical to the development of solid-state batteries. The effects of mechanochemical synthesis that lead to increased ionic conductivity in an archetypical sodium-ion conductor Na3PS4 are not fully understood. We present here a comprehensive analysis based on diffraction (Bragg, pair distribution function), spectroscopy (impedance, Raman, NMR, INS) and ab-initio simulations aimed at elucidating the synthesis-property relationships in Na3PS4. We consolidate previously reported interpretations about the local structure of ball-milled samples, underlining the sodium disorder and showing that a local tetragonal framework more accurately describes the structure than the originally proposed cubic one. Through variable-pressure impedance spectroscopy measurements, we report for the first time the activation volume for Na+ migration in Na3PS4, which is ~30% higher for the ball-milled samples. Moreover, we show that the effect of ball-milling on increasing the ionic conductivity of Na3PS4 to ~10-4 S/cm can be reproduced by applying external pressure on a sample from conventional high temperature ceramic synthesis. We conclude that the key effects of mechanochemical synthesis on the properties of solid electrolytes can be analyzed and understood in terms of pressure, strain and activation volume.
Published: 2020

49. Molecular Nanocrystals on Ultrathin NaCl Films on Au(111)

Author: Yongfeng Wang, Jörg Kröger, Hao Tang, Richard Berndt, Peking University [Beijing], Christian-Albrechts-Universität zu Kiel (CAU), Centre d'élaboration de matériaux et d'études structurales (CEMES), Université Toulouse III - Paul Sabatier (UT3), Université Fédérale Toulouse Midi-Pyrénées-Université Fédérale Toulouse Midi-Pyrénées-Centre National de la Recherche Scientifique (CNRS)-Institut de Chimie de Toulouse (ICT-FR 2599), Institut National Polytechnique (Toulouse) (Toulouse INP), Université Fédérale Toulouse Midi-Pyrénées-Université Fédérale Toulouse Midi-Pyrénées-Centre National de la Recherche Scientifique (CNRS)-Institut de Recherche pour le Développement (IRD)-Université Toulouse III - Paul Sabatier (UT3), Université Fédérale Toulouse Midi-Pyrénées-Institut de Chimie du CNRS (INC)-Institut National Polytechnique (Toulouse) (Toulouse INP), Université Fédérale Toulouse Midi-Pyrénées-Centre National de la Recherche Scientifique (CNRS)-Institut de Recherche pour le Développement (IRD)-Institut de Chimie du CNRS (INC)-Institut National des Sciences Appliquées - Toulouse (INSA Toulouse), Institut National des Sciences Appliquées (INSA)-Institut National des Sciences Appliquées (INSA), Institut National des Sciences Appliquées - Toulouse (INSA Toulouse), Institut National des Sciences Appliquées (INSA)-Université de Toulouse (UT)-Institut National des Sciences Appliquées (INSA)-Université de Toulouse (UT)-Institut de Chimie de Toulouse (ICT), Institut de Recherche pour le Développement (IRD)-Université Toulouse III - Paul Sabatier (UT3), Université de Toulouse (UT)-Université de Toulouse (UT)-Institut de Chimie du CNRS (INC)-Centre National de la Recherche Scientifique (CNRS)-Institut National Polytechnique (Toulouse) (Toulouse INP), Université de Toulouse (UT)-Institut de Recherche pour le Développement (IRD)-Université Toulouse III - Paul Sabatier (UT3), Université de Toulouse (UT)-Institut de Chimie du CNRS (INC)-Centre National de la Recherche Scientifique (CNRS)-Institut National Polytechnique (Toulouse) (Toulouse INP), and Université de Toulouse (UT)-Centre National de la Recherche Scientifique (CNRS)
Subjects: Indoles, Nanostructure, Surface Properties, chemistry.chemical_element, 02 engineering and technology, Isoindoles, Sodium Chloride, 010402 general chemistry, 01 natural sciences, Biochemistry, Catalysis, Colloid and Surface Chemistry, Adsorption, Organometallic Compounds, Molecule, Particle Size, ComputingMilieux_MISCELLANEOUS, Group 2 organometallic chemistry, Molecular Structure, Intermolecular force, Membranes, Artificial, General Chemistry, 021001 nanoscience & nanotechnology, Nanostructures, 0104 chemical sciences, Crystallography, chemistry, Nanocrystal, Tin, Gold, Particle size, [CHIM.OTHE]Chemical Sciences/Other, 0210 nano-technology
Abstract: Direct comparison of SnPc growth on a metal and a nearly insulating surface was achieved by adsorption of SnPc on Au(111) partially covered with NaCl. While on Au(111), SnPc lies flat and grows in a Stranski-Krastanov mode; on NaCl, Volmer-Weber growth of three-dimensional molecular nanocrystals occurs. On NaCl, intermolecular interactions dominate over the molecule-NaCl coupling and result in a tilted adsorption configuration.
Published: 2010

50. Roles of Iron Complexes in Catalytic Radical Alkene Cross-Coupling: A Computational and Mechanistic Study

Author: Rinaldo Poli, Patrick L. Holland, Dongyoung Kim, S. M. Wahidur Rahaman, Brandon Q. Mercado, Yale University [New Haven], Laboratoire de chimie de coordination (LCC), Institut National Polytechnique (Toulouse) (Toulouse INP), Université Fédérale Toulouse Midi-Pyrénées-Université Fédérale Toulouse Midi-Pyrénées-Université Toulouse III - Paul Sabatier (UT3), Université Fédérale Toulouse Midi-Pyrénées-Institut de Chimie de Toulouse (ICT-FR 2599), Université Fédérale Toulouse Midi-Pyrénées-Université Fédérale Toulouse Midi-Pyrénées-Centre National de la Recherche Scientifique (CNRS)-Institut de Recherche pour le Développement (IRD)-Université Toulouse III - Paul Sabatier (UT3), Université Fédérale Toulouse Midi-Pyrénées-Institut de Chimie du CNRS (INC)-Centre National de la Recherche Scientifique (CNRS)-Institut de Recherche pour le Développement (IRD)-Institut de Chimie du CNRS (INC)-Centre National de la Recherche Scientifique (CNRS), National Science Foundation (CHE-1465017), National Institutes of Health (GM129081), Humboldt Foundation, and Centre National de la Recherche Scientifique (CNRS)
Subjects: Free Radicals, Alkenes, 010402 general chemistry, 01 natural sciences, Biochemistry, Article, Catalysis, Coupling reaction, Electron Transport, Colloid and Surface Chemistry, Computational chemistry, Molecule, [CHIM.COOR]Chemical Sciences/Coordination chemistry, Density Functional Theory, chemistry.chemical_classification, Ethanol, Molecular Structure, Hydride, Chemistry, Alkene, General Chemistry, Hydrogen atom, 0104 chemical sciences, Catalytic cycle, Density functional theory, Stress, Mechanical, Protons, Iron Compounds, Hydrogen
Abstract: International audience; A growing and useful class of alkene coupling reactions involve hydrogen atom transfer (HAT) from a metal-hydride species to an alkene to form a free radical, which is responsible for subsequent bond formation. Here, we use a combination of experimental and computational investigations to map out the mechanistic details of iron-catalyzed reductive alkene cross-coupling, an important representative of the HAT alkene reactions. We are able to explain several observations that were previously mysterious. First, the rate-limiting step in the catalytic cycle is the formation of the reactive Fe–H intermediate, elucidating the importance of the choice of reductant. Second, the success of the catalytic system is attributable to the exceptionally weak (17 kcal/mol) Fe–H bond, which performs irreversible HAT to alkenes in contrast to previous studies on isolable hydride complexes where this addition was reversible. Third, the organic radical intermediates can reversibly form organometallic species, which helps to protect the free radicals from side reactions. Fourth, the previously accepted quenching of the postcoupling radical through stepwise electron transfer/proton transfer is not as favorable as alternative mechanisms. We find that there are two feasible pathways. One uses concerted proton-coupled electron transfer (PCET) from an iron(II) ethanol complex, which is facilitated because the O–H bond dissociation free energy is lowered by 30 kcal/mol upon metal binding. In an alternative pathway, an O-bound enolate-iron(III) complex undergoes proton shuttling from an iron-bound alcohol. These kinetic, spectroscopic, and computational studies identify key organometallic species and PCET steps that control selectivity and reactivity in metal-catalyzed HAT alkene coupling, and create a firm basis for elucidation of mechanisms in the growing class of HAT alkene cross-coupling reactions.
Published: 2019

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