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.