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Establishing unprecedented types of bonding interactions is one of the fundamental challenges in synthetic chemistry, paving the way to new (electronic) structures, physicochemical properties, and reactivity. In this context, unsupported element‐element interactions are particularly noteworthy since they offer pristine scientific information about the newly identified structural motif. Here we report the synthesis, isolation, and full characterization of the heterobimetallic Bi/Pt compound [Pt(PCy3)2(BiMe2)(SbF6)] (1), bearing the first unsupported transition metal→bismuth donor/acceptor interaction as its key structural motif. 1 is surprisingly robust, its electronic spectra are interpreted in a fully relativistic approach, and it reveals an unprecedented reactivity towards H2. [ABSTRACT FROM AUTHOR]

Establishing unprecedented types of bonding interactions is one of the fundamental challenges in synthetic chemistry, paving the way to new (electronic) structures, physicochemical properties, and reactivity. In this context, unsupported element‐element interactions are particularly noteworthy since they offer pristine scientific information about the newly identified structural motif. Here we report the synthesis, isolation, and full characterization of the heterobimetallic Bi/Pt compound [Pt(PCy3)2(BiMe2)(SbF6)] (1), bearing the first unsupported transition metal→bismuth donor/acceptor interaction as its key structural motif. 1 is surprisingly robust, its electronic spectra are interpreted in a fully relativistic approach, and it reveals an unprecedented reactivity towards H2. [ABSTRACT FROM AUTHOR]

Establishing unprecedented types of bonding interactions is one of the fundamental challenges in synthetic chemistry, paving the way to new (electronic) structures, physicochemical properties, and reactivity. In this context, unsupported element‐element interactions are particularly noteworthy since they offer pristine scientific information about the newly identified structural motif. Here we report the synthesis, isolation, and full characterization of the heterobimetallic Bi/Pt compound [Pt(PCy3)2(BiMe2)(SbF6)] (1), bearing the first unsupported transition metal→bismuth donor/acceptor interaction as its key structural motif. 1 is surprisingly robust, its electronic spectra are interpreted in a fully relativistic approach, and it reveals an unprecedented reactivity towards H2. [ABSTRACT FROM AUTHOR]

Establishing unprecedented types of bonding interactions is one of the fundamental challenges in synthetic chemistry, paving the way to new (electronic) structures, physicochemical properties, and reactivity. In this context, unsupported element‐element interactions are particularly noteworthy since they offer pristine scientific information about the newly identified structural motif. Here we report the synthesis, isolation, and full characterization of the heterobimetallic Bi/Pt compound [Pt(PCy3)2(BiMe2)(SbF6)] (1), bearing the first unsupported transition metal→bismuth donor/acceptor interaction as its key structural motif. 1 is surprisingly robust, its electronic spectra are interpreted in a fully relativistic approach, and it reveals an unprecedented reactivity towards H2. [ABSTRACT FROM AUTHOR]

When bismuth atoms are incorporated into cyclic organic systems, this commonly goes along with strained or distorted molecular geometries, which can be exploited to modulate the physical and chemical properties of these compounds. In six‐membered heterocycles, bismuth atoms are often accompanied by oxygen, sulfur or nitrogen as a second hetero‐element. In this work, we present the first examples of six‐membered rings, in which two CH units are replaced by BiX moieties (X=Cl, Br, I), resulting in dihydro‐anthracene analogs. Their behavior in chemically reversible reduction reactions is explored, aiming at the generation of dibisma‐anthracene (bismanthrene). Heterometallic compounds (Bi/Fe, Bi/Mn) are introduced as potential bismanthrene surrogates, as supported by bismanthrene‐transfer to selenium. Analytical techniques used to investigate the reported compounds include NMR spectroscopy, high‐resolution mass spectrometry, single‐crystal X‐ray diffraction analyses, and DFT calculations. [ABSTRACT FROM AUTHOR]

Bimetallic Compounds. An unsupported Pt‐Bi donor‐acceptor interaction and its umpolung by reaction with H2 is reported by Antti J. Karttunen, Jordi Poater, Crispin Lichtenberg et al in their Communication (e202410291). [ABSTRACT FROM AUTHOR]

Bimetallic Compounds. An unsupported Pt‐Bi donor‐acceptor interaction and its umpolung by reaction with H2 is reported by Antti J. Karttunen, Jordi Poater, Crispin Lichtenberg et al in their Communication (e202410291). [ABSTRACT FROM AUTHOR]

Bimetallic Compounds. An unsupported Pt‐Bi donor‐acceptor interaction and its umpolung by reaction with H2 is reported by Antti J. Karttunen, Jordi Poater, Crispin Lichtenberg et al in their Communication (e202410291)...By Johannes Schwarzmann; Toni Eskelinen; Sascha Reith; Jacqueline Ramler; Antti J. Karttunen; Jordi Poater and Crispin LichtenbergReported by Author; Author; Author; Author; Author; Author; Author [Extracted from the article]

Bimetallic Compounds. An unsupported Pt‐Bi donor‐acceptor interaction and its umpolung by reaction with H2 is reported by Antti J. Karttunen, Jordi Poater, Crispin Lichtenberg et al in their Communication (e202410291)...By Johannes Schwarzmann; Toni Eskelinen; Sascha Reith; Jacqueline Ramler; Antti J. Karttunen; Jordi Poater and Crispin LichtenbergReported by Author; Author; Author; Author; Author; Author; Author [Extracted from the article]

Copyright of Angewandte Chemie is the property of Wiley-Blackwell and its content may not be copied or emailed to multiple sites or posted to a listserv without the copyright holder's express written permission. However, users may print, download, or email articles for individual use. This abstract may be abridged. No warranty is given about the accuracy of the copy. Users should refer to the original published version of the material for the full abstract. (Copyright applies to all Abstracts.)

Copyright of Angewandte Chemie is the property of Wiley-Blackwell and its content may not be copied or emailed to multiple sites or posted to a listserv without the copyright holder's express written permission. However, users may print, download, or email articles for individual use. This abstract may be abridged. No warranty is given about the accuracy of the copy. Users should refer to the original published version of the material for the full abstract. (Copyright applies to all Abstracts.)

Bimetallic Compounds. An unsupported Pt‐Bi donor‐acceptor interaction and its umpolung by reaction with H2 is reported by Antti J. Karttunen, Jordi Poater, Crispin Lichtenberg et al in their Communication (e202410291)...By Johannes Schwarzmann; Toni Eskelinen; Sascha Reith; Jacqueline Ramler; Antti J. Karttunen; Jordi Poater and Crispin LichtenbergReported by Author; Author; Author; Author; Author; Author; Author [Extracted from the article]

Bimetallic Compounds. An unsupported Pt‐Bi donor‐acceptor interaction and its umpolung by reaction with H2 is reported by Antti J. Karttunen, Jordi Poater, Crispin Lichtenberg et al in their Communication (e202410291)...By Johannes Schwarzmann; Toni Eskelinen; Sascha Reith; Jacqueline Ramler; Antti J. Karttunen; Jordi Poater and Crispin LichtenbergReported by Author; Author; Author; Author; Author; Author; Author [Extracted from the article]

The diorgano(bismuth)alcoholate [Bi((C6H4CH2)2S)OPh] (1‐OPh) has been synthesized and fully characterized. Stoichiometric reactions, UV/Vis spectroscopy, and (TD‐)DFT calculations suggest its susceptibility to homolytic and heterolytic Bi−O bond cleavage under given reaction conditions. Using the dehydrocoupling of silanes with either TEMPO or phenol as model reactions, the catalytic competency of 1‐OPh has been investigated (TEMPO=(tetramethyl‐piperidin‐1‐yl)‐oxyl). Different reaction pathways can deliberately be addressed by applying photochemical or thermal reaction conditions and by choosing radical or closed‐shell substrates (TEMPO vs. phenol). Applied analytical techniques include NMR, UV/Vis, and EPR spectroscopy, mass spectrometry, single‐crystal X‐ray diffraction analysis, and (TD)‐DFT calculations. [ABSTRACT FROM AUTHOR]

Keywords: bismuth; cationic species; Lewis acidity; Lewis pair formation EN bismuth cationic species Lewis acidity Lewis pair formation 1 1 1 05/30/23 20230526 NES 230526 B Bi Lewis acidic b : Donor-free cationic bismuth compounds readily coordinate Lewis basic substrates including arenes, phosphanes, and isonitriles, and degrade the weakly coordinating counter-anion [PF SB 6 sb ] SP - sp . Bismuth, cationic species, Lewis acidity, Lewis pair formation In the graphic, a bismuth kraken grabs Lewis basic substrates, solving scientific puzzles about bismuth-based Lewis acidity. [Extracted from the article]

Establishing unprecedented types of bonding interactions is one of the fundamental challenges in synthetic chemistry, paving the way to new (electronic) structures, physicochemical properties, and reactivity. In this context, unsupported element-element interactions are particularly noteworthy since they offer pristine scientific information about the newly identified structural motif. Here we report the synthesis, isolation, and full characterization of the heterobimetallic Bi/Pt compound [Pt(PCy 3 ) 2 (BiMe 2 )(SbF 6 )] (1), bearing the first unsupported transition metal→bismuth donor/acceptor interaction as its key structural motif. 1 is surprisingly robust, its electronic spectra are interpreted in a fully relativistic approach, and it reveals an unprecedented reactivity towards H 2 ., (© 2024 The Authors. Angewandte Chemie International Edition published by Wiley-VCH GmbH.)

When bismuth atoms are incorporated into cyclic organic systems, this commonly goes along with strained or distorted molecular geometries, which can be exploited to modulate the physical and chemical properties of these compounds. In six-membered heterocycles, bismuth atoms are often accompanied by oxygen, sulfur or nitrogen as a second hetero-element. In this work, we present the first examples of six-membered rings, in which two CH units are replaced by BiX moieties (X=Cl, Br, I), resulting in dihydro-anthracene analogs. Their behavior in chemically reversible reduction reactions is explored, aiming at the generation of dibisma-anthracene (bismanthrene). Heterometallic compounds (Bi/Fe, Bi/Mn) are introduced as potential bismanthrene surrogates, as supported by bismanthrene-transfer to selenium. Analytical techniques used to investigate the reported compounds include NMR spectroscopy, high-resolution mass spectrometry, single-crystal X-ray diffraction analyses, and DFT calculations., (© 2023 The Authors. Chemistry - A European Journal published by Wiley-VCH GmbH.)

The molecular compound [BiDipp 2 (SbF 6 )], containing the bulky, donor-free bismuth cation [BiDipp 2 ] + has been synthesized and fully characterized (Dipp=2,6-iPr 2 -C 6 H 3 ). Using its methyl analog [BiMe 2 (SbF 6 )] as a second reference point, the impact of steric bulk on bismuth-based Lewis acidity was investigated in a combined experimental (Gutmann-Beckett and modified Gutmann-Beckett methods) and theoretical approach (DFT calculations). Reactivity studies of the bismuth cations towards [PF 6 ] - and neutral Lewis bases such as isocyanides C≡NR' revealed facile fluoride ion abstraction and straightforward Lewis pair formation, respectively. The first examples of compounds featuring bismuth-bound isocyanides have been isolated and fully characterized., (© 2023 The Authors. Chemistry - A European Journal published by Wiley-VCH GmbH.)

The synthesis, photophysical, and electrochemical properties of selectively mono-, bis- and tris-dimethylamino- and trimethylammonium-substituted bis-triarylborane bithiophene chromophores are presented along with the water solubility and singlet oxygen sensitizing efficiency of the cationic compounds Cat 1+ , Cat 2+ , Cat(i) 2+ , and Cat 3+ . Comparison with the mono-triarylboranes reveals the large influence of the bridging unit on the properties of the bis-triarylboranes, especially those of the cationic compounds. Based on these preliminary investigations, the interactions of Cat 1+ , Cat 2+ , Cat(i) 2+ , and Cat 3+ with DNA, RNA, and DNApore were investigated in buffered solutions. The same compounds were investigated for their ability to enter and localize within organelles of human lung carcinoma (A549) and normal lung (WI38) cells showing that not only the number of charges but also their distribution over the chromophore influences interactions and staining properties., (© 2021 The Authors. Chemistry - A European Journal published by Wiley-VCH GmbH.)

A series of bis(σ)-borane complexes of Group 6 transition metals were prepared by direct dihydroborane coordination to the metal center. Reaction of [M(CO) 3 (PCy 3 ) 2 ] and two dihydroboranes [DurBH 2 ] and [(Me 3 Si) 2 NBH 2 ] (Dur=2,3,5,6-Me 4 C 6 H) yielded bis(σ)-borane complexes fac-[M(CO) 3 (PCy 3 ){η 2 -(H 2 BR)}] (R=Dur; 1: M=Cr, 2: M=W; R=N(SiMe 3 ) 2 ; 3: M=Cr, 4: M=W). In the case of molybdenum, we have isolated an arene complex (5) with [DurBH 2 ] in which the Dur group acts as a η 6 -bound ligand, and with [(Me 3 Si) 2 NBH 2 ] a similar bis(σ)-borane complex was isolated, cis,trans-[Mo(CO) 2 (PCy 3 ) 2 {η 2 -(H 2 BN(SiMe 3 ) 2 }] (6), with a different pattern of auxiliary ligands. The complexes were investigated by multinuclear NMR spectroscopy, mass spectrometry, X-ray diffraction analysis, and computational methods. Quantum theory of atoms in molecules (QTAIM) calculations demonstrated that the borane complexes may be described as pure bis(σ)-borane complexes rather than elongated or stretched examples given that the calculations do not show the presence of a ring-critical point (RCP) at the ring formed by the interactions of the B-H with metal center., (© 2019 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.)