Metalation-induced denitrogenative reductive coupling of isocyanides on a silylene-bridged nickel cluster

Abstract

The denitrogenative reductive coupling of two molecules of CNtBu to afford a disilylketenimine with an aza-disilacyclobutane skeleton was achieved on a multinuclear silylene-bridged Ni cluster framework in the absence of any strong reducing reagents. During this reaction, sequential cleavage of a C=N bond and formation of a C C bond involving two molecules of CNtBu were achieved on a nickel cluster surrounded by four silylene moieties. First, the cleavage of the C N bond of one molecule of CNtBu provided a silylene-supported carbide and an NtBu moiety on the dinuclear nickel skeleton. Further metalation induced coupling between the carbide moiety and an additional molecule of CNtBu on the pentanuclear nickel-cluster framework to form a moiety via formation of a C C bond. Thermolysis of this pentanuclear cluster produced a disilylketenimine with an aza-disilacyclobutane skeleton in 58% yield.