Ultrafast Infrared Mechanistic Studies of the Interaction of 1-Hexyne with Group 6 Hexacarbonyl Complexes
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- 作者：Jennifer E. Shanoski ; Christine K. Payne ; Matthias F. Kling ; Elizabeth A. Glascoe ; and Charles B. Harris
- 刊名：Organometallics
- 出版年：2005
- 出版时间：April 11, 2005
- 年：2005
- 卷：24
- 期：8
- 页码：1852 - 1859
- 全文大小：164K
- 年卷期：v.24,no.8(April 11, 2005)
- ISSN：1520-6041
文摘
The ultrafast solvation and rearrangement dynamics following the photolysis of M(CO)6(M = Cr, Mo, W) in terminal alkyne solutions have been investigated. Upon photoinitiatedloss of a ligand from the parent metal hexacarbonyl, coordination to an alkyne solventmolecule is followed by rearrangement to a complex that is bound to the terminal alkynesite in a 
chars/pi.gif" BORDER=0 >-bonded fashion. This rearrangement occurs on a time scale that is anticorrelatedwith the metal-ligand binding energy. A dissociative rearrangement is ruled out for thisprocess in favor of an associative or interchange mechanism. Previous theoretical andexperimental studies are examined, and we conclude that the ultimate rearrangement to avinylidene species is energetically inaccessible at ambient temperatures on the femtosecondto millisecond time scale.
chars/pi.gif" BORDER=0 >-bonded fashion. This rearrangement occurs on a time scale that is anticorrelatedwith the metal-ligand binding energy. A dissociative rearrangement is ruled out for thisprocess in favor of an associative or interchange mechanism. Previous theoretical andexperimental studies are examined, and we conclude that the ultimate rearrangement to avinylidene species is energetically inaccessible at ambient temperatures on the femtosecondto millisecond time scale.