Evidence for a Carbonyl-Containing Intermediate in the 308-nm Photolysis of trans-RhCl(CO)(PMe3)2
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- 作者：R. Krishnan and Richard H. Schultz
- 刊名：Inorganic Chemistry
- 出版年：2005
- 出版时间：September 19, 2005
- 年：2005
- 卷：44
- 期：19
- 页码：6691 - 6694
- 全文大小：57K
- 年卷期：v.44,no.19(September 19, 2005)
- ISSN：1520-510X
文摘
Time-resolved infrared absorption spectroscopy is used to monitor the events during the first ~100 
s following308-nm photolysis of trans-RhCl(CO)(PMe3)2 (I) in a C6D6 or Decalin solution. Upon photolysis, the intensity of thecarbonyl stretching absorption of I decreases and a new C-O stretching absorption (A) appears at 2006 cm-1 inC6D6 (2013 cm-1 in Decalin). Within ~100 s, A disappears concurrently with partial regeneration of I and oxidativeaddition of a solvent C-D (C-H) bond. Our observation of the prompt formation of a carbonyl-containing intermediatecontrasts 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 Iare discussed.
s following308-nm photolysis of trans-RhCl(CO)(PMe3)2 (I) in a C6D6 or Decalin solution. Upon photolysis, the intensity of thecarbonyl stretching absorption of I decreases and a new C-O stretching absorption (A) appears at 2006 cm-1 inC6D6 (2013 cm-1 in Decalin). Within ~100 s, A disappears concurrently with partial regeneration of I and oxidativeaddition of a solvent C-D (C-H) bond. Our observation of the prompt formation of a carbonyl-containing intermediatecontrasts 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 Iare discussed.