Author: Pitteri Bruno Bortoluzzi Marco
Publisher: Springer Publishing Company
ISSN: 0340-4285
Source: Transition Metal Chemistry, Vol.31, Iss.8, 2006-11, pp. : 1028-1033
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Abstract
The kinetics of the process AuCl3(nu) + Cl−→ AuCl 4− + nu (nu = one of a number of five-membered N-donor heterocycles covering a wide range of basicity, namely: oxazole, 2,4,5-trimethyloxazole, thiazole, 5-methylthiazole, 4-methylthiazole, 4,5-dimethylthiazole, 2,4-dimethylthiazole, 2,4,5-trimethylthiazole, imidazole and 2-methylimidazole) have been studied in methanol at 25 °C. The reactions follow the usual two-term rate law, rate = (k 1 + k 2[Cl−])[complex], observed in a square-planar substitution associative-mechanism. The second-order rate constants, k 2, indicate that the discriminating ability of Au(III) in these complexes is good and markedly influenced by the nature of the leaving group. A linear-free-energy relationship, logk 2 = 0.53pk
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