Author:
Chen Lezhan,Poë Anthony J.
Abstract
The kinetics have been studied of reactions of the cluster Ru3(CO)11 (P(OEt)3) with a variety of P- and As-donor nucleophiles, L, in alkane solution. Reactions proceed according to the rate equation: kobsd = k1 + k2 [L] and activation parameters for the two paths have been obtained. When combined with activation parameters for Ru3(CO)12 and some other Ru3(CO)11L′ clusters the values of [Formula: see text] and [Formula: see text] are found to lie on a good isokinetic plot. The changes in the activation parameters are consistent with major and systematic changes in the nature of the Ru3(CO)10L′ moieties left after CO dissociation.Analysis of the dependence of log k2 on the electronic and steric nature of the various nucleophiles leads to the derivation of electronic and steric profiles that are characteristic of the cluster, together with values for the intrinsic or standard susceptibility of the cluster towards nucleophilic attack. These kinetic characteristics are compared with those similarly derived for Ru3(CO)12. Keywords: metal carbonyls, ruthenium, clusters, kinetics, mechanisms.
Publisher
Canadian Science Publishing
Subject
Organic Chemistry,General Chemistry,Catalysis
Cited by
21 articles.
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