Abstract
AbstractThe first 16 valence electron [bis(NHC)](silylene)Ni0 complex 1, [(TMSL)ClSi:→Ni(NHC)2], bearing the acyclic amido‐chlorosilylene (TMSL)ClSi: (TMSL=N(SiMe3)Dipp; Dipp=2,6‐Pri2C6H4) and two NHC ligands (N‐heterocyclic carbene=:C[(Pri)NC(Me)]2) was synthesized in high yield and structurally characterized. Compound 1 is capable of facile dihydrogen activation under ambient conditions to give the corresponding HSi‐NiH complex 2. Most notably, 1 reacts with catechol borane to afford the unprecedented hydroborylene‐coordinated (chloro)(silyl)nickel(II) complex 3, {[cat(TMSL)Si](Cl)Ni←:BH(NHC)2}, via the cleavage of two B−O bonds and simultaneous formation of two Si−O bonds. The mechanism for the formation of 3 was rationalized by means of DFT calculations, which highlight the powerful synergistic effects of the Si:→Ni moiety in the breaking of incredibly strong B−O bonds.
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