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Updated: Sep 26, 2025

Imine Metathesis by Silica-Supported Catalysts Using the Methodology of Surface Organometallic Chemistry
Published on: October 18, 2019
Metalation-induced denitrogenative reductive coupling of isocyanides on a silylene-bridged nickel cluster
Kento Shimamoto1, Yusuke Sunada1,2,3
1Department of Applied Chemistry, School of Engineering, The University of Tokyo 4-6-1, Komaba Meguro-ku Tokyo 153-8505 Japan.
Abstract:
The denitrogenative reductive coupling of two molecules of CN Bu 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[triple bond, length as m-dash]N bond and formation of a C[triple bond, length as m-dash]C bond involving two molecules of CN Bu were achieved on a nickel cluster surrounded by four silylene moieties. First, the cleavage of the C[triple bond, length as m-dash]N bond of one molecule of CN Bu provided a silylene-supported carbide and an N Bu moiety on the dinuclear nickel skeleton. Further metalation induced coupling between the carbide moiety and an additional molecule of CN Bu on the pentanuclear nickel-cluster framework to form a moiety via formation of a C[triple bond, length as m-dash]C bond. Thermolysis of this pentanuclear cluster produced a disilylketenimine with an aza-disilacyclobutane skeleton in 58% yield.
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