A Bis(silylene)‐Substituted ortho‐Carborane as a Superior Ligand in the Nickel‐Catalyzed Amination of Arenes |
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| Authors: | Yu‐Peng Zhou Dr Saeed Raoufmoghaddam Dr Tibor Szilvási Prof?Dr Matthias Driess |
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| Affiliation: | 1. Technische Universit?t Berlin, Department of Chemistry: Metalorganics and Inorganic Materials, Sekr. C2, Berlin, Germany;2. Department of Inorganic and Analytical Chemistry, Budapest University of Technology and Economics, Budapest, Hungary |
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| Abstract: | The synthesis and structure of the first 1,2‐bis(NHSi)‐substituted ortho‐carborane (LSi:)C]2B10H10 (termed SiCCSi) is reported (NHSi=N‐heterocyclic silylene; L=PhC(NtBu)2). Its suitability to serve as a reliable bis(silylene) chelating ligand for transition metals is demonstrated by the formation of SiCCSi]NiBr2 and SiCCSi]Ni(CO)2 complexes. The CO stretching vibration modes of the latter indicate that the SiII atoms in the SiCCSi ligand are even stronger σ donors than the PIII atoms in phosphines and CII atoms in N‐heterocyclic carbene (NHC) ligands. Moreover, the strong donor character of the SiCCSi] ligand enables SiCCSi]NiBr2 to act as an outstanding precatalyst (0.5 mol % loading) in the catalytic aminations of arenes, surpassing the activity of previously known molecular Ni‐based precatalysts (1–10 mol %). |
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| Keywords: | homogeneous catalysis N-heterocyclic silylenes ligand design nickel o-carboranes |
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