Catalysts for selective aerobic oxidation under ambient conditions - Advances in Catalytic Activation of Dioxygen by Metal Complexes - page 235

6. EMPIRICAL REACTION RATE LAW

Typical kinetic curves of CEES consumption and CEESO formation are
presented in Figure 1. The dotted, dashed and solid lines in Figure 1 arise
from fitting of experimental data to the proposed mechanism and are
discussed below. While it may not be readily apparent, the kinetics of the
main reaction after the induction period does not obey any simple kinetic
law. The reaction gradually slows down as a result of a mild inhibition by
CEESO product. The dotted line is a simple exponential assuming no such
inhibition takes place.
The primary experimentally determined rate parameter was
+d[CEESO]/dt, but -d[CEES]/dt and were also evaluated in many
cases. These values are indicated henceforth as "rate". The reaction rate was
determined as a function of the concentrations of CEES, Au(III), Ag(I),
together in a constant 1:2:1 mole ratio, DMSO
as a model for the CEESO product and

Figures 2-4 and Table 2 give the rate dependencies of the main reaction,
eq 1, on the concentrations of CEES, total Au(III),
and DMSO. The maximum rate is achieved at Au : : ratio 1:2:1,
suggesting that the dominant transition state complex contains one and

two groups. Further, it was established that replacement of by
or generated species with little or no catalytic activity.
In contrast, replacement of by formed a more reactive complex,
confirming a significant and specific role for (or in the active
catalyst (Figure 2). The rate increases with the concentration of the thioether