The first silylone-3d-metal complexes, LSiCu(NacNacM) (2) [L = 1,2-(RSi)2-1,2-C2B10H10, R = PhC(NtBu)2; NacNacM = HC(CMeNMes)2, Mes = 2,4,6-Me3-C6H2] and LSiNi(NacNacD) (3) [NacNacD = 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 [(NacNacMCu)2benzene] and [(NacNacDNi)2toluene], respectively. Density Functional Theory (DFT) analyses reveal that complex 2 features a Si0→CuI dative bond, while 3 exhibits a Si0→NiI bond. Oxidation of the Si0–NiI species 3 with [Cp2Fe]+ occurs at the Ni site to form the [3]+ cation with a Si0→NiII coordination.

https://pubs.rsc.org/en/Content/ArticleLanding/2025/CC/D5CC02098K