C-H bond activation by unsymmetrical 2-(N-arylimino)pyrrolide Pt complexes: geometric effects on reactivity

Carl N Iverson; Charles A G Carter; R Tom Baker; John D Scollard; Jay A Labinger; John E Bercaw

doi:10.1021/ja036511d

C-H bond activation by unsymmetrical 2-(N-arylimino)pyrrolide Pt complexes: geometric effects on reactivity

J Am Chem Soc. 2003 Oct 22;125(42):12674-5. doi: 10.1021/ja036511d.

Authors

Carl N Iverson¹, Charles A G Carter, R Tom Baker, John D Scollard, Jay A Labinger, John E Bercaw

Affiliation

¹ Los Alamos Catalysis Initiative, Chemistry Division, MS J514, Los Alamos National Laboratory, Los Alamos, New Mexico 87545, USA. bakertom@lanl.gov

PMID: 14558792
DOI: 10.1021/ja036511d

Abstract

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 degrees 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.