Substituent exchange between an imino(silyl)silylene and aryl isocyanides

Isocyanides, being isoelectronic and isolobal to carbon monoxide, are an important class of compounds in organic synthesis and coordination chemistry. In terms of reactivity, the severing of R–NC bonds has gained particular interest recently, as the cleaved moieties can be used as a CN/R source in cross-coupling reactions. Herein, we disclose Ar–NC bond cleavage and subsequent transformation of aryl isocyanides to silylcyanide and diaryldiiminodisilenes, utilizing the ambiphilic acyclic imino(silyl)silylene 1. A proposed reaction mechanism for the aryl and silyl group exchange, based on experimental evidence and supported by quantum chemical calculations, proposes an initial insertion of aryl isocyanide into the Si–Si bond of 1 and a subsequent aryl transfer to the silylene center via aryl C–N bond cleavage.