Sequential Homo‐ and Hetero‐Coupling of Isocyanide and Carbon Monoxide Mediated by Acyclic Imino(silyl)Silylene

Abstract

ABSTRACT Carbon monoxide (CO) and its isoelectronic analogues, isocyanides (RNC), have been extensively employed as model substrates to elucidate elementary steps of the Fischer–Tropsch (F–T) process, particularly those governing C–C bond construction. Building on this concept, we demonstrate carbon chain growth mediated by an acyclic imino(hypersilyl)silylene through sequential reactions with CO and isocyanides, ultimately affording well‐defined C 6 frameworks composed of four isocyanide and two CO units. A proposed mechanism for the homo‐ and hetero‐coupling processes, derived from experimental observations and corroborated by quantum chemical calculations, reveals that the silylene functions as an initiator, inducing the stepwise homocoupling of RNC through consecutive formation of electrophilic sites, as well as promoting heterocoupling reactions with CO.