American Chemical Society
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C−H Bond Activation by Unsymmetrical 2-(N-Arylimino)pyrrolide Pt Complexes:  Geometric Effects on Reactivity

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posted on 2003-09-24, 00:00 authored by Carl N. Iverson, Charles A. G. Carter, R. Tom Baker, John D. Scollard, Jay A. Labinger, John E. Bercaw
Reactions of chloroplatinum methyl complexes with N-(arylimino)pyrrolide anions afford cis and trans neutral platinum methyl complexes. Isomers with methyl trans to the pyrrolide nitrogen activate benzene C−H bonds at 85 °C more than 80 times faster than the corresponding cis isomer. In addition, reactions of platinum dimethyl complexes with N-(arylimino)pyrroles (Ar = 4-substituted phenyl) in C6D6 at ambient temperature give unlabeled methane and cis methyl complex containing heavily deuterated Pt−Me. In contrast, bulky aryl substituents give methane isotopomers and trans-Pt−Ph product. The origins of these observations are discussed.