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19 F NMR parameters are versatile probes for studying metal-fluoride complexes. Quantum chemical calculations of 19 F NMR chemical shifts enhance the accuracy and validity of the resonance signal assignments in complex spectra. However, the treatment of solvation effects in these calculations remains challenging. In this study, we establish a successful computational protocol using ab initio molecular dynamics simulations for the accurate prediction of 19 F NMR chemical shifts in square-planar nickel-fluoride complexes. In particular, we have studied in detail the trans -[NiF(2,3,4,5-C 6 F 4 I)(PEt 3 ) 2 ] complex in a benzene solution. Our computations revealed that accounting for the dynamic conformational flexibility of the complex, including intramolecular interactions, is crucial for obtaining reliable 19 F NMR chemical shifts. Overall, this study advances the understanding of employing state-of-the-art quantum chemistry methods to accurately model 19 F NMR chemical shifts of nickel-fluoride complexes, emphasizing the importance of addressing solvation effects in such calculations.

Enzymes in nature, such as the copper-based lytic polysaccharide monooxygenases (LPMOs), have gained significant attention for their exceptional performance in C-H activation reactions. The use of H 2 O 2 by LPMOs enzymes has also increased the interest in understanding the oxidation mechanism promoted by this oxidant. While some literature proposes Fenton-like chemistry involving the formation of Cu(II)-OH species and the hydroxyl radical, others contend that Cu(I) activation by H 2 O 2 yields a Cu(II)-oxyl intermediate. In this study, we focused on a bioinspired Cu(I) complex to investigate the reaction mechanism of its oxidation by H 2 O 2 using density functional theory and ab initio molecular dynamics simulations. The latter approach was found to be critical for finding the key Cu intermediates. Our results show that the highly flexible coordination environment of copper strongly influences the nature of the oxidized Cu(II) species. Furthermore, they suggest the favorable formation of trans- Cu(II)-(OH) 2 moieties in low-coordinated Cu(II) species. This trans configuration hinders the formation of Cu(II)-oxyl species, facilitating intramolecular H-abstraction reactions in line with experimentally observed ligand oxidation processes.

We have employed computational methods to investigate the iridium-catalyzed allylic substitution leading to the formation of enantioenriched allyl carbamates from carbon dioxide (CO 2 ). The reaction occurs in several steps, with initial formation of an iridium-allyl, followed by nucleophilic attack by the carbamate formed in situ from CO 2 and an amine. A detailed isomeric analysis shows that the rate-determining step differs for the ( R )- and ( S )-pathways. These insights are essential for understanding reactions involving enantioselective formation of allyl carbamates from CO 2 ., Competing Interests: The authors declare no competing financial interest., (© 2024 The Authors. Published by American Chemical Society.)

In recent years, considerable progress has been made in the conversion of biomass into renewable chemicals, yet the range of value-added products that can be formed from biomass remains relatively small. Herein, we demonstrate that molecules available from biomass serve as viable starting materials for the synthesis of phosphine ligands, which can be used in homogeneous catalysis. Specifically, we prepared renewable analogues of Beller's ligand (di(1-adamantyl)- n -butylphosphine, cataCXium® A), which is widely used in homogeneous catalysis. Our new renewable phosphine ligands facilitate Pd-catalysed Suzuki-Miyaura, Stille, and Buchwald-Hartwig coupling reactions with high yields, and our catalytic results can be rationalized based on the stereoelectronic properties of the ligands. The new phosphine ligands generate catalytic systems that can be applied for the late-stage functionalization of commercial drugs., Competing Interests: There are no conflicts to declare., (This journal is © The Royal Society of Chemistry.)

Ab initio molecular dynamics simulations are used to explore tetrahydrofuran (THF) solutions containing pure LiCl and LiCl with CH 3 MgCl, as model constituents of the turbo Grignard reagent. LiCl aggregates as Li 4 Cl 4 , which preferentially assumes compact cubane-like conformations. In particular, an open-edge pseudotetrahedral frame is promoted by solvent-assisted Li-Cl bond cleavage. Among the Grignard species involved in the Schlenk equilibrium, LiCl prefers to coordinate MgCl 2 through μ 2 -Cl bridges. Using a 1:1 Li:Mg ratio, the plastic tetranuclear LiCl cluster decomposes to a highly solvated mixed LiCl·MgCl 2 aggregate with prevalent Li-(μ 2 -Cl) 2 -Mg rings and linear LiCl entities. The MgCl 2 -assisted disaggregation of Li 4 Cl 4 occurs through transient structures analogous to those detected for pure LiCl in THF, also corresponding to moieties observed in the solid state. This study identifies a synergistic role of LiCl for the determination of the compounds present in turbo Grignard solutions. LiCl shifts the Schlenk equilibrium promoting a higher concentration of dialkylmagnesium, while decomposing into smaller, more soluble, mixed Li:Mg:Cl clusters.

The halogen bond (XB) is a highly directional class of noncovalent interactions widely explored by experimental and computational studies. However, the NMR signature of the XB has attracted limited attention. The prediction and analysis of the solid-state NMR (SSNMR) chemical shift tensor provide useful strategies to better understand XB interactions. In this work, we employ a computational protocol for modeling and analyzing the 19 F SSNMR chemical shifts previously measured in a family of square-planar trans Ni II -L 2 -iodoaryl-fluoride (L = PEt 3 ) complexes capable of forming self-complementary networks held by a NiF···I(C) halogen bond [Thangavadivale, V.; Chem. Sci. 2018, 9, 3767-3781]. To understand how the 19 F NMR resonances of the nickel-bonded fluoride are affected by the XB, we investigate the origin of the shielding in trans -[NiF(2,3,5,6-C 6 F 4 I)(PEt 3 ) 2 ], trans -[NiF(2,3,4,5-C 6 F 4 I)(PEt 3 ) 2 ], and trans -[NiF(C 6 F 5 )(PEt 3 ) 2 ] in the solid state, where a XB is present in the two former systems but not in the last. We perform the 19 F NMR chemical shift calculations both in periodic and molecular models. The results show that the crystal packing has little influence on the NMR signatures of the XB, and the NMR can be modeled successfully with a pair of molecules interacting via the XB. Thus, the observed difference in chemical shift between solid-state and solution NMR can be essentially attributed to the XB interaction. The very high shielding of the fluoride and its driving contributor, the most shielded component of the chemical shift tensor, are well reproduced at the 2c-ZORA level. Analysis of the factors controlling the shielding shows how the highest occupied Ni/F orbitals shield the fluoride in the directions perpendicular to the Ni-F bond and specifically perpendicular to the coordination plane. This shielding arises from the magnetic coupling of the Ni(3d)/F(2p lone pair) orbitals with the vacant σ Ni-F * orbital, thereby rationalizing the very highly upfield (shielded) resonance of the component (δ 33 ) along this direction. We show that these features are characteristic of square-planar nickel-fluoride complexes. The deshielding of the fluoride in the halogen-bonded systems is attributed to an increase in the energy gap between the occupied and vacant orbitals that are mostly responsible for the paramagnetic terms, notably along the most shielded direction.

Selective reduction of CO 2 is an efficient solution for producing nonfossil-based chemical feedstocks and simultaneously alleviating the increasing atmospheric concentration of this greenhouse gas. With this aim, molecular electrocatalysts are being extensively studied, although selectivity remains an issue. In this work, a combined experimental-computational study explores how the molecular structure of Mn-based complexes determines the dominant product in the reduction of CO 2 to HCOOH, CO, and H 2 . In contrast to previous Mn(bpy-R)(CO) 3 Br catalysts containing alkyl amines in the vicinity of the Br ligand, here, we report that bpy-based macrocycles locking these amines at the side opposite to the Br ligand change the product selectivity from HCOOH to H 2 . Ab initio molecular dynamics simulations of the active species showed that free rotation of the Mn(CO) 3 moiety allows for the approach of the protonated amine to the reactive center yielding a Mn-hydride intermediate, which is the key in the formation of H 2 and HCOOH. Additional studies with DFT methods showed that the macrocyclic moiety hinders the insertion of CO 2 to the metal hydride favoring the formation of H 2 over HCOOH. Further, our results suggest that the minor CO product observed experimentally is formed when CO 2 adds to Mn on the side opposite to the amine ligand before protonation. These results show how product selectivity can be modulated by ligand design in Mn-based catalysts, providing atomistic details that can be leveraged in the development of a fully selective system., Competing Interests: The authors declare no competing financial interest., (© 2023 The Authors. Published by American Chemical Society.)

Platinum-based anticancer drugs are actively developed utilizing lipophilic ligands or drug carriers for the efficient penetration of biomembranes, reduction of side effects, and tumor targeting. We report the development of a supramolecular host-guest system built on cationic platinum(II) compounds bearing ligands anchored in the cavity of the macrocyclic host. The host-guest binding and hydrolysis process on the platinum core were investigated in detail by using NMR, MS, X-ray diffraction, and relativistic DFT calculations. The encapsulation process in cucurbit[7]uril unequivocally promotes the stability of hydrolyzed dicationic cis -[Pt II (NH 3 ) 2 (H 2 O)(NH 2 -R)] 2+ compared to its trans isomer. Biological screening on the ovarian cancer lines A2780 and A2780/CP shows time-dependent toxicity. Notably, the reported complex and its β-cyclodextrin (β-CD) assembly achieve the same cellular uptake as cisplatin and cisplatin@β-CD, respectively, while maintaining a significantly lower toxicity profile.

1 H NMR spectroscopy has become an important technique for the characterization of transition-metal hydride complexes, whose metal-bound hydrides are often difficult to locate by X-ray diffraction. In this regard, the accurate prediction of 1 H NMR chemical shifts provides a useful, but challenging, strategy to help in the interpretation of the experimental spectra. In this work, we establish a density-functional-theory protocol that includes relativistic, solvent, and dynamic effects at a high level of theory, allowing us to report an accurate and reliable interpretation of 1 H NMR hydride chemical shifts of iridium polyhydride complexes. In particular, we have studied in detail the hydride chemical shifts of the [Ir 6 (IMe) 8 (CO) 2 H 14 ] 2+ complex in order to validate previous assignments. The computed 1 H NMR chemical shifts are strongly dependent on the relativistic treatment, the choice of the DFT exchange-correlation functional, and the conformational dynamics. By combining a fully relativistic four-component electronic-structure treatment with ab initio molecular dynamics, we were able to reliably model both the terminal and bridging hydride chemical shifts and to show that two NMR hydride signals were inversely assigned in the experiment.

The incarceration of o-benzyne and 27 other guest molecules within hemicarcerand 1, as reported experimentally by Warmuth, and Cram and co-workers, has been studied by density functional theory (DFT). The 1 H NMR chemical shifts, rotational mobility, and conformational preference of the guests within the supramolecular cage were determined, which showed intriguing correlations of the chemical shifts with structural parameters of the host-guest system. Furthermore, based on the computed chemical shifts reassignments of some NMR signals are proposed. This affects, in particular, the putative characterization of the volatile benzyne molecule inside a hemicarcerand, for which our CCSD(T) and KT2 results indicate that the experimentally observed signals are most likely not resulting from an isolated o-benzyne within the supramolecular host. Instead, it is shown that the guest reacted with an aromatic ring of the host, and this adduct is responsible for the experimentally observed signals., (© 2019 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.)

The transfer hydrogenation of N-heterocyclic carbene (NHC)-supported diborenes with dimethylamine borane proceeds with high selectivity for the trans-1,2-dihydrodiboranes. DFT calculations, supported by kinetic studies and deuteration experiments, suggest a stepwise proton-first-hydride-second reaction mechanism via an intermediate μ-hydrodiboronium dimethylaminoborate ion pair., (© 2019 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.)

We report a combined experimental-theoretical study on the 31P NMR chemical shift for a number of trans-platinum(ii) complexes. Validity and reliability of the 31P NMR chemical shift calculations are examined by comparing with the experimental data. A successful computational protocol for the accurate prediction of the 31P NMR chemical shifts was established for trans-[PtCl2(dma)PPh3] (dma = dimethylamine) complexes. The reliability of the computed values is shown to be critically dependent on the level of relativistic effects (two-component vs. four component), choice of density functionals, dynamical averaging, and solvation effects. Snapshots obtained from ab initio molecular dynamics simulations were used to identify those solvent molecules which show the largest interactions with the platinum complex, through inspection by using the non-covalent interaction program. We observe satisfactory accuracy from the full four-component matrix Dirac-Kohn-Sham method (mDKS) based on the Dirac-Coulomb Hamiltonian, in conjunction with the KT2 density functional, and dynamical averaging with explicit solvent molecules.

In the present study, we have theoretically analyzed supramolecular complexes based on the Watson-Crick A-T and A-U base pairs using dispersion-corrected density functional theory (DFT). Hydrogen atoms H8 and/or H6 in the natural adenine and thymine/uracil bases were replaced, respectively, by substituents X8, Y6 = NH - , NH 2 , NH 3 + (N series), O - , OH, OH 2 + (O series), F, Cl or Br (halogen series). We examined the effect of the substituents on the hydrogen-bond lengths, strength and bonding mechanism, and the NMR shielding constants of the C2-adenine and C2-thymine/uracil atoms in the base pairs. The general belief in the literature that there is a direct connection between changes in the hydrogen-bond strength and the C2-adenine shielding constant is conclusively rejected by our computations.

Inverse carbon-free sandwich structures with formula E2P4 (E=Al, Ga, In, Tl) have been proposed as a promising new target in main-group chemistry. Our computational exploration of their corresponding potential-energy surfaces at the S12h/TZ2P level shows that indeed stable carbon-free inverse-sandwiches can be obtained if one chooses an appropriate Group 13 element for E. The boron analogue B2P4 does not form the D(4h)-symmetric inverse-sandwich structure, but instead prefers a D(2d) structure of two perpendicular BP2 units with the formation of a double B-B bond. For the other elements of Group 13, Al-Tl, the most favorable isomer is the D(4h) inverse-sandwich structure. The preference for the D(2d) isomer for B2P4 and D(4h) for their heavier analogues has been rationalized in terms of an isomerization-energy decomposition analysis, and further corroborated by determination of aromaticity of these species., (© 2014 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.)

We report here a systematic study on the ability of molecular cages to bind (transition) metals. Starting from the superferrocenophane we investigate the incorporation of first-row transition metal (Sc-Zn) and alkaline-earth metal (Mg, Ca) double cations into these supermetallocenophane (super[5]phane) cages, and compare them with the corresponding metallocenes (Inorg. Chim. Acta, 2007, 360, 179). Moreover, we also investigate the binding of neutral and double-cationic metals inside supermetallocyclophane (super[6]phane) cages. The heterolytic and homolytic associations show preferences for different metals, and new metal-containing cages are proposed that should be viable candidates for synthesis.

A series of clusters with the general formula CBe(5)E(-) (E = Al, Ga, In, Tl) are theoretically shown to have a planar pentacoordinate carbon atom. The structures show a simple and rigid topological framework-a planar EBe(4) ring surrounding a C center, with one of the ring Be-Be bonds capped in-plane by a fifth Be atom. The system is stabilized by a network of multicenter σ bonds in which the central C atom is the acceptor, and π systems as well by which the C atom donates charge to the Be and E atoms that encircle it.