Bulletin of the Chemical Society of Japan
Online ISSN : 1348-0634
Print ISSN : 0009-2673
ISSN-L : 0009-2673
Kinetics and Mechanism of the Oxidation Reaction of Bis(μ-dibutyldithiocarbamato-S,S′)-digold(I) by Halogens
Hidetoshi KitaKazuyuki ItohKoji TanakaToshio Tanaka
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1978 Volume 51 Issue 12 Pages 3530-3533


Kinetics of the reaction of bis(μ-dibutyldithiocarbamato-S,S′)-digold(I), [Au(n-Bu2dtc)]2, with I2, IBr, and Br2 in dichloromethane was studied by the stopped-flow technique. A 1 : 1 charge-transfer (CT) complex, [Au(n-Bu2dtc)]2·X2 (X2=I2, IBr, and Br2), formed in the initial process of reaction was identified spectrophotometrically at −50 °C. The rates of reaction were almost the same for I2, IBr, and Br2, and independent of the both [Au(n-Bu2dtc)]2 and halogen concentrations. The reaction has been interpreted to proceed via the charge-transfer complex, [Au(n-Bu2dtc)]2·X2, which decomposes in a rate-determining step to give the final product, [AuIII(n-Bu2dtc)2][AuIX2]. The activation parameters for the reactions were determined: ΔH\ eweq(kJ/mol)=43.7 (I2), 26.0 (IBr), and 12.3 (Br2); ΔS\ eweq(J/mol K))=−91.5 (I2), −156 (IBr), and −201 (Br2).

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