title: The influence of gold(i) on the mechanism of thiolate, disulfide exchange.
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.
authors.affiliation: University of Maine, Department of Chemistry, Orono, ME 04469-5706, USA. abruce@maine.edu mbruce@maine.edu.
authors.forename: Gamage S P
authors.initials: GS
authors.lastname: Garusinghe
authors.forename: S Max
authors.initials: SM
authors.lastname: Bessey
authors.forename: Alice E
authors.initials: AE
authors.lastname: Bruce
authors.forename: Mitchell R M
authors.initials: MR
authors.lastname: Bruce