On the use of “fast kinetics” to determine the mechanism of ligand substitution at a solvated transition-metal intermediate

✍ Scribed by Richard H. Schultz

• Publisher: John Wiley and Sons
• Year: 2004
• Tongue: English
• Weight: 113 KB
• Volume: 36
• Category: Article
• ISSN: 0538-8066
• DOI: 10.1002/kin.20007

✦ Synopsis

Abstract

Substitution of the weakly‐coordinated solvent molecule at a solvated transition‐metal intermediate is frequently investigated by “fast kinetic” methods. In typical experiments, the kinetics of the reaction are determined by following the time dependence of the changes in the reaction mixture's UV‐visible or infrared spectrum following photolytic creation of the intermediate. We consider the two limiting mechanisms (associative and dissociative), as well as the case of competition between them, and show that under typical “fast kinetics” experimental conditions, the different mechanisms are kinetically indistinguishable. © 2004 Wiley Periodicals, Inc. Int J Chem Kinet 36: 427–433, 2004