Metalation-induced denitrogenative reductive coupling of isocyanides on a silylene-bridged nickel cluster. Issue 14 (22nd March 2022)

• Record Type: Journal Article
• Authors: Shimamoto, Kento; Sunada, Yusuke
• Is Part Of: Chemical science. Volume 13:Issue 14(2022)
• Page Start: 4115
• Page End: 4121
• Publication Date: 2022-03-22
• Subjects: Chemistry -- Periodicals; 540.5
• DOI: 10.1039/d1sc06935g
• Languages: English
• ISSNs: 2041-6520

Abstract

Abstract : The denitrogenative reductive coupling of two molecules of CN t Bu was achieved on a multinuclear silylene-bridged Ni cluster framework, and two possible intermediary Ni clusters were isolated. Abstract : The denitrogenative reductive coupling of two molecules of CN t 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N bond and formation of a CC bond involving two molecules of CN t Bu were achieved on a nickel cluster surrounded by four silylene moieties. First, the cleavage of the CN bond of one molecule of CN t Bu provided a silylene-supported carbide and an N t Bu moiety on the dinuclear nickel skeleton. Further metalation induced coupling between the carbide moiety and an additional molecule of CN t Bu 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.