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

Abstract

The denitrogenative reductive coupling of two molecules of CN^tBu 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 CN bond and formation of a CC bond involving two molecules of CN^tBu were achieved on a nickel cluster surrounded by four silylene moieties. First, the cleavage of the CN bond of one molecule of CN^tBu provided a silylene-supported carbide and an N^tBu moiety on the dinuclear nickel skeleton. Further metalation induced coupling between the carbide moiety and an additional molecule of CN^tBu on the pentanuclear nickel-cluster framework to form a moiety via formation of a CC bond. Thermolysis of this pentanuclear cluster produced a disilylketenimine with an aza-disilacyclobutane skeleton in 58% yield.