Premium
Ligand Effects on the Reactivity of Cu I L Complexes Towards Cl 3 CCO 2 −
Author(s) -
Navon Nadav,
Burg Ariela,
Cohen Haim,
van Eldik Rudi,
Meyerstein Dan
Publication year - 2002
Publication title -
european journal of inorganic chemistry
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 0.667
H-Index - 136
eISSN - 1099-0682
pISSN - 1434-1948
DOI - 10.1002/1099-0682(20022)2002:2<423::aid-ejic423>3.0.co;2-g
Subject(s) - chemistry , steric effects , redox , reactivity (psychology) , ligand (biochemistry) , chlorine , aqueous solution , reaction mechanism , kinetics , reaction rate , photochemistry , computational chemistry , inorganic chemistry , stereochemistry , catalysis , organic chemistry , physics , pathology , quantum mechanics , medicine , biochemistry , alternative medicine , receptor
The effect of the nature of the ligand L on the mechanism and kinetics of the reaction of Cu I L with Cl 3 CCO 2 − in aqueous solution is reported. The results demonstrate that the rate of the chlorine abstraction reaction, which is usually the rate‐determining step in the process, is affected by: a) the redox potential of the Cu II/I L couple, b) the hybridization on Cu I in the Cu I L complex, c) steric hindrance, d) electron density on the central Cu I cation, at the binding site of the chlorine atom to be abstracted. Measurement of Δ V ≠ for the chlorine abstraction step indicates that this reaction proceeds by the inner‐sphere mechanism, as expected. When the redox potential of the Cu II/I L couple is considerably cathodically shifted the transient complex LCu II −CCl 2 CO 2 − is relatively long‐lived.