Evidence for a carbonyl-containing intermediate in the 308-nm photolysis of trans-RhCl(CO)(PMe3)2

R Krishnan; Richard H Schultz

doi:10.1021/ic050219k

Evidence for a carbonyl-containing intermediate in the 308-nm photolysis of trans-RhCl(CO)(PMe3)2

Inorg Chem. 2005 Sep 19;44(19):6691-4. doi: 10.1021/ic050219k.

Authors

R Krishnan¹, Richard H Schultz

Affiliation

¹ Department of Chemistry, Bar-Ilan University, Ramat-Gan, Israel.

PMID: 16156627
DOI: 10.1021/ic050219k

Abstract

Time-resolved infrared absorption spectroscopy is used to monitor the events during the first approximately 100 mus following 308-nm photolysis of trans-RhCl(CO)(PMe3)2 (I) in a C6D6 or Decalin solution. Upon photolysis, the intensity of the carbonyl stretching absorption of I decreases and a new C-O stretching absorption (A) appears at 2006 cm(-1) in C6D6 (2013 cm(-1) in Decalin). Within approximately 100 mus, A disappears concurrently with partial regeneration of I and oxidative addition of a solvent C-D (C-H) bond. Our observation of the prompt formation of a carbonyl-containing intermediate contrasts with prior observations that photolysis at longer wavelengths leads solely to dissociation of CO from I. The implications of the observation of A for the understanding of the mechanisms of photocatalytic reactions of I are discussed.