Premium
On the use of “fast kinetics” to determine the mechanism of ligand substitution at a solvated transition‐metal intermediate
Author(s) -
Schultz Richard H.
Publication year - 2004
Publication title -
international journal of chemical kinetics
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 0.341
H-Index - 68
eISSN - 1097-4601
pISSN - 0538-8066
DOI - 10.1002/kin.20007
Subject(s) - chemistry , kinetics , associative substitution , limiting , molecule , substitution reaction , transition metal , photochemistry , reaction mechanism , ligand (biochemistry) , kinetic energy , transition state , computational chemistry , catalysis , organic chemistry , mechanical engineering , biochemistry , physics , receptor , quantum mechanics , engineering
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