Unprecedented bis(silylene)-supported silylone–metal complexes with Si0→CuI, Si0→NiI, and Si0→NiII dative bonds

Abstract

The first silylone-3d-metal complexes, LSiCu(NacNac^M) (2) [L = 1,2-(RSi)₂-1,2-C₂B₁₀H₁₀, R = PhC(NtBu)₂; NacNac^M = HC(CMeNMes)₂, Mes = 2,4,6-Me₃-C₆H₂] and LSiNi(NacNac^D) (3) [NacNac^D = HC(CMeNDipp)₂, Dipp = 2,6-iPr₂-C₆H₃], are reported, resulting from the reaction of the strongly σ-donating and chelating bis(silylenyl)-ortho-carborane silylone LSi⁰ with [(NacNac^MCu)₂benzene] and [(NacNac^DNi)₂toluene], respectively. Density Functional Theory (DFT) analyses reveal that complex 2 features a Si⁰→Cu^I dative bond, while 3 exhibits a Si⁰→Ni^I bond. Oxidation of the Si⁰–Ni^I species 3 with [Cp₂Fe]⁺ occurs at the Ni site to form the [3]⁺ cation with a Si⁰→Ni^II coordination.