The reactions between
trans-[Au(CN)
2
X
2
]
-
(X = Cl or Br) and Me
2
S have been studied by
conventional and high-pressure stopped-flow spectrophotometry in acidic
aqueous solution containing 10% (w/w) methanol. The overall
stoichiometry Au
III
∶Me
2
S is
1∶(1.0 ± 0.1) in agreement with the reaction:
trans-[Au(CN)
2
X
2
]
-
+ Me
2
S +
H
2
O → [Au(CN)
2
]
-
+ Me
2
SO + 2H
+
+ 2X
-
. Initial rapid substitution
processes result in the formation of a pre-equilibrium between transient
gold(III) complexes, which are reduced to
[Au(CN)
2
]
-
in a subsequent slower redox
process. Complexes trans-[Au(CN)
2
X(Me
2
S)]
with an asymmetric electron distribution along the X–Au–S
axis are reduced rapidly via an intermolecular process, in
which Me
2
S attacks a co-ordinated halide. The complex
trans-[Au(CN)
2
(Me
2
S)
2
]
, on the other hand, undergoes slow reduction to
gold(I) involving a water molecule. The rapid halide-mediated
oxidation of thioethers implies that reduction of metal ions in
biological systems by such moieties should be favoured in extracellular
environments, where the chloride concentrations are high.