(NHC)Si═C═N-R: A Two-Coordinated Si⁰-Isocyanide Compound as Si(NHC) Transfer Reagent

Experimental and theoretical studies are reported of the first two-coordinated Si⁰-isocyanide compound (SIDipp)Si═C═N-Ar^Mes (1: SIDipp (NHC) = C[N(Dipp)CH₂]₂, Ar^Mes = 2,6-dimesitylphenyl), supported by an N-heterocyclic carbene (NHC). A Si atom economic two-step synthesis of 1 involves a 2e reduction of the isocyanide-stabilized silyliumylidene salt [SiBr(CNAr^Mes)(SIDipp)][B(Ar^F)₄] (2[B(Ar^F)₄], Ar^F = B(C₆H₃-3,5-(CF₃)₂)₄) with KC₈. 2[B(Ar^F)₄] was obtained from SiBr₂(SIDipp) after bromide abstraction with an equimolar mixture of Na[B(Ar^F)₄] and Ar^MesNC. Exact adherence to the stoichiometry is crucial in the latter reaction, since 2[B(Ar^F)₄] reacts with SiBr₂(SIDipp) via isocyanide exchange to afford the disilicon(II) salt [Si₂Br₃(SIDipp)₂)][B(Ar^F)₄] (3[B(Ar^F)₄]), the reaction leading to an equilibrium that favors 3[B(Ar^F)₄] (K_eq(298 K) = 10.6, ΔH° = -10.6 kJ mol^-1; ΔS^° = -16.0 J mol^-1 K^-1). 3[B(Ar^F)₄] was obtained selectively from the 2:1 reaction of SiBr₂(SIDipp) with Na[B(Ar^F)₄] and fully characterized. Detailed studies of 1 reveal an intriguing structure featuring a planar C_NHC-Si-C-N skeleton with a V-shaped geometry at the dicoordinated Si⁰ center, a slightly bent Si═C═N core, a C_NHC-Si-C_CNR 3c-2e out of plane π-bond (HOMO), and an anticlinal conformation of the SIDipp and Ar^Mes substituents leading to axial chirality and the presence of two enantiomers, (R)-1 and (S)-1. Compound 1 displays structural dynamics in solution, rapidly interconverting the enantiomers. The silacumulene 1 is a potent Si(SIDipp) transfer agent as demonstrated by the synthesis and full characterization of the NHC-supported germasilyne (Z)-(SIDipp)(Cl)Si═GeAr^Mes (4) from 1 and Ge(Ar^Mes)Cl.