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Issue 28, 2016
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The influence of gold(I) on the mechanism of thiolate, disulfide exchange

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Abstract

The mechanism of gold(I)-thiolate, disulfide exchange was investigated by using initial-rate kinetic studies, 2D (1H–1H) ROESY NMR spectroscopy, and electrochemical/chemical techniques. The rate law for exchange is overall second order, first order in gold(I)-thiolate and disulfide. 2D NMR experiments show evidence of association between gold(I)-thiolate and disulfide. Electrochemical/chemical investigations do not show evidence of free thiolate and are consistent with a mechanism involving formation of a [Au–S, S–S], four-centered metallacycle intermediate during gold(I)-thiolate, disulfide exchange.

Graphical abstract: The influence of gold(i) on the mechanism of thiolate, disulfide exchange

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The article was received on 11 Apr 2016, accepted on 20 Jun 2016 and first published on 21 Jun 2016


Article type: Communication
DOI: 10.1039/C6DT01400C
Citation: Dalton Trans., 2016,45, 11261-11266

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    The influence of gold(I) on the mechanism of thiolate, disulfide exchange

    G. S. P. Garusinghe, S. M. Bessey, A. E. Bruce and M. R. M. Bruce, Dalton Trans., 2016, 45, 11261
    DOI: 10.1039/C6DT01400C

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