C-H bond activation by unsymmetrical 2-(N-arylimino)pyrrolide Pt complexes: geometric effects on reactivity.
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.
Iverson
Carl N
CN
Los Alamos Catalysis Initiative, Chemistry Division, MS J514, Los Alamos National Laboratory, Los Alamos, New Mexico 87545, USA. bakertom@lanl.gov
Carter
Charles A G
CA
Baker
R Tom
RT
Scollard
John D
JD
Labinger
Jay A
JA
Bercaw
John E
JE