title: Evidence for a carbonyl-containing intermediate in the 308-nm photolysis of trans-RhCl(CO)(PMe3)2.
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.
authors.affiliation: Department of Chemistry, Bar-Ilan University, Ramat-Gan, Israel.
authors.forename: R
authors.initials: R
authors.lastname: Krishnan
authors.forename: Richard H
authors.initials: RH
authors.lastname: Schultz