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Recent advances on carborane-based ligands in low-valent group 13 and group 14 elements chemistry

Chinese Chemical Letters 2022年第8期33卷 3672-3680页

作者： Hao Wang School of chemistry and Chemical Engineering Southeast UniversityNanjing 211189China

Carboranes are a class of polyhedral boron-carbon molecular clusters,they can serve as versatile ligands in stabilizing low-valent main group element compounds,due to their exceptionally thermal and chemical stabilities,easy modifications at the cage carbon vertices,as well as large spherical steric *** carborane-based ligands provide interesting opportunities for the synthesis of low-valent main group element compounds with novel structure and reactivity,which indeed enrich the chemistry of low-valent element main group *** review summarizes the recent advances in the chemistry of lowvalent group 13 and group 14 element compounds supported by carborane-based *** and perspectives in this new and flourishing field are discussed in this review.

关键词： Carborane Borylene Carbene Silylene main group chemistry

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Synthesis of a Mixed Silylene–Carbene Chelate Ligand from an N-Heterocyclic Silylcarbene Mediated by Nickel

Synthesis of a Mixed Silylene–Carbene Chelate Ligand from a...

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中国化学会第九届全国无机化学学术会议

作者： Gengwen Tan Matthias Driess Xinping Wang Department of chemistry Nanjing University Department of chemistry Technische Universitt Berlin

N-heterocyclic carbenes（NHCs） represent one of the most widely utilized supporting ligands in transition metal（TM） chemistry in the last decades.[1] These complexes have exhibited numerous superior activities in comparison to phosphine complexes owing to the stronger σ donor ability of NHC ligands.[2] Whereas, the heavy homologs of NHCs, the N-heterocyclic silylenes（NHSis） are emerging as a novel class of versatile steering ligands in the coordination chemistry of the transition metals, and their complexes have already shown remarkable features in small molecule activation and as precatalysts for various types of organic transformations.[3] Therefore, combining these two ligand types in one chelate molecule might enable new coordination features at TMs. Moreover, the presence of both strong σ-donating moieties might facilitate the coordination and dissociation of other ligands thereby improving the reactivity or catalytic performance of respective TM *** I present the unexpectedly facile formation of the first mixed NHSi-NHC chelate complex[L1Si:（CH2）（NHC）]NiBr2 2 [L1 = CH（Me C=NAr）2, Ar = 2,6-iP r2C6H3;NHC =3,4,5-trimethylimidazol-2-yliden-6-yl] through the hydrogen atom migration from the silicon atom to the exocyclic methylene group in L2Si（H）（CH2）NHC [L2 = CH（C=CH2）（CMe）（NAr）2, Ar = 2,6-iPr2C6H3;NHC =3,4,5-trimethylimidazol-2-yliden-6-yl] mediated by Ni Br2. The analogous reduction of 2 in the presence of1,2-bis（dimethylphosphino）ethane（DMPE） furnishes the first mixed NHSi-NHC（DMPE）Ni0 complex 3. Moreover,complex 2 shows a high catalytic activity for Kumada-Corriu-type cross-coupling reactions.[4]

关键词： silylene main group chemistry N-heterocyclic carbene homogeneous catalysis cross-coupling reaction

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