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Dalton Trans. 2016 Jul 28;45(28):11261-6. doi: 10.1039/c6dt01400c. Epub 2016 Jun 29.

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

Dalton transactions (Cambridge, England : 2003)

Gamage S P Garusinghe, S Max Bessey, Alice E Bruce, Mitchell R M Bruce

Affiliations

  1. University of Maine, Department of Chemistry, Orono, ME 04469-5706, USA. [email protected] [email protected].

PMID: 27353236 DOI: 10.1039/c6dt01400c

Abstract

The mechanism of gold(i)-thiolate, disulfide exchange was investigated by using initial-rate kinetic studies, 2D ((1)H-(1)H) 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.

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