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

R. Krishnan, Richard H. Schultz

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Abstract

Time-resolved infrared absorption spectroscopy is used to monitor the events during the first ∼100 μs 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 ∼100 μs, 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.

Original languageEnglish
Pages (from-to)6691-6694
Number of pages4
JournalInorganic Chemistry
Volume44
Issue number19
DOIs
StatePublished - 19 Sep 2005

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