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

The denitrogenative reductive coupling of two molecules of CNtBu to afford a disilylketenimine with an azadisilacyclobutane 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 equivalent to C bond and formation of a C equivalent to C bond involving two molecules of (CNBu)-Bu-t were achieved on a nickel cluster surrounded by four silylene moieties. First, the cleavage of the C equivalent to C bond of one molecule of (CNBu)-Bu-t provided a silylene-supported carbide and an (NBu)-Bu-t moiety on the dinuclear nickel skeleton. Further metalation induced coupling between the carbide moiety and an additional molecule of (CNBu)-Bu-t on the pentanuclear nickel-cluster framework to form a (mu(3)-eta(2)-R3Si - C equivalent to C - NR2) moiety via formation of a C equivalent to C bond. Thermolysis of this pentanuclear cluster produced a disilylketenimine with an azadisilacyclobutane skeleton in 58% yield.

Automated summary

The denitrogenative reductive coupling of CNtBu to afford a disilylketenimine with an azadisilacyclobutane skeleton was achieved on a multinuclear silylene-bridged Ni cluster framework. This reaction provides a new strategy for the efficient synthesis of organic compounds without the use of strong reducing reagents.