3 years ago

Silylene–Nickel Promoted Cleavage of B−O Bonds: From Catechol Borane to the Hydroborylene Ligand

Silylene–Nickel Promoted Cleavage of B−O Bonds: From Catechol Borane to the Hydroborylene Ligand
Matthias Driess, Tibor Szilvási, Terrance J. Hadlington
The 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. Si–Ni cooperativity: The first 16 valence electron amido-chlorosilylene nickel(0) complex 1 readily activates H2 to give the hydrido(silyl)nickel(II) complex 2. With catechol borane, 1 affords the deep-blue hydroborylene nickel(II) complex 3, the first example of a hydroborylene metal complex and is the result of SiII−Ni0 cooperativity in the B−O bond activation processes.

Publisher URL: http://onlinelibrary.wiley.com/resolve/doi

DOI: 10.1002/anie.201702772

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