Reactions of Anilines and Benzamides with a Fourteen-Electron Iridium(I) Bis(Phosphinite) Complex: N-H Oxidative Addition versus Lewis Base Coordination.

ABSTRACT: Anilines react with (POCOP)Ir(C(6)H(5))(H), 12, (POCOP = 2,6-(OPtBu(2))(2)C(6)H(3)) to yield equilibrium mixtures of 12, the Ir(I) sigma-complexes (POCOP)Ir(NH(2)Ar), 13, and the Ir(III) oxidative addition adducts (POCOP)Ir(H)(NHAr), 14. Quantitative studies of these equilibria for a series of anilines were carried out. Anilines possessing electron-withdrawing groups favor the Ir(III) oxidative addition adduct over the Ir(I) sigma complex. Low temperature studies using p-chloroaniline show that the Ir(I) sigma-complex is the kinetic product of reaction and is likely the precursor to the Ir(III) oxidative addition adduct. Reductive elimination of complexes 14 in the presence of ethylene led to the corresponding anilines and the ethylene complex (POCOP)Ir(C(2)H(4)). Kinetic analysis of these

SUBMITTER: Sykes AC 

PROVIDER: S-EPMC2600712 | biostudies-literature | 2006 Mar

REPOSITORIES: biostudies-literature