Flash Communication: Selective Benzylidene Insertion Reactions in Organoplatinum Complexes

The reaction of PhCHBr₂ with the cycloneophylplatinum complex [Pt(CH₂CMe₂C₆H₄)(NN)], 1, NN = 4,4’-di-t-butyl-2,2’-bipyridine (bubipy), gave the complex [PtBr₂(CH₂CMe₂C₆H₄CHPh)(NN)], 2, which is formed by formal oxidative insertion of benzylidene, PhCH, into the arylplatinum bond of 1. By monitoring the reactions by ¹H NMR spectroscopy, intermediates were detected and shown to be products of oxidative addition [PtBr(CHBrPh)(CH₂CMe₂C₆H₄CHPh)(NN)], 3, along with a side product [PtBr₂(CH₂CMe₂C₆H₄)(NN)]. The formation of 2 gives the first example of selective benzylidene insertion reactions into an aryl–platinum bond, with potential for applications in catalysis.