Author:
Chung H. L.,Bounsall E. J.
Abstract
The base hydrolysis of trans-[Rh(cyclam)XY]+ (cyclam = 1,4,8,11-tetraazacyclotetradecane; X− and Y− = Cl−, Br−, and I−) are studied in aqueous solution over a range of OH− concentration and at various temperatures. The kinetics are done at a constant ionic strength with excess of [OH−] (smallest ratio = 200:1) so that pseudo first order rate constants are obtained for all the determinations. All of the reactions proceed with complete retention of configuration, and no trans-to-cis isomerization is found. The kinetic trans effect of these complexes is I− > Br− > Cl− on a rate basis, but based on ΔH≠, I− > Br− = Cl−. These Rh(III) complexes exhibit kinetic class (b) character on the ΔH≠ basis. The results of the rate constants and the activation parameters are interpreted in ternis of an SN1CB mechanism. The behavior of these complexes is compared to that of the other analogous complexes.
Publisher
Canadian Science Publishing
Subject
Organic Chemistry,General Chemistry,Catalysis
Cited by
9 articles.
订阅此论文施引文献
订阅此论文施引文献，注册后可以免费订阅5篇论文的施引文献，订阅后可以查看论文全部施引文献
1. Synthesis and X-ray structure of a monoprotonated salt and of three transition-metal complexes of N,N′-ditertiobutyl-2,11-diaza[3.3](2,6)pyridinophane;Polyhedron;2001-09
2. The Crystal and Molecular Structure ofcis-Dichloro[3,11-dimethyl-3,11,17,18-tetraazatricyclo[11.3.1.15,9]octadeca-1(17),5,7,9(18),13,15-hexaene]rhodium(III) Cation;Bulletin of the Chemical Society of Japan;1990-06
3. Mechanisms of reactions of metal complexes: Some recent developments;Transition Metal Chemistry;1987-04
4. Proton exchange and base-catalysed hydrolysis of some trans- and cis-dichloro(1,4,8,11-tetra-azacyclotetradecane) complexes of chromium(III), ruthenium(III), and rhodium(III);Journal of the Chemical Society, Dalton Transactions;1986
5. Thermodynamic and kinetic data for cation-macrocycle interaction;Chemical Reviews;1985-08