Catalysts for selective aerobic oxidation under ambient conditions - Advances in Catalytic Activation of Dioxygen by Metal Complexes - page 241

Combining eqs 11, 16 and 17 gives eqs 18 and 19 for the reaction rate.

Eq 19 has been used to fit the experimental data, namely the
dependencies of rate versus [CEES] and The best fit is a solid

curve shown in Figure 4 with and

The errors were estimated at the 95% confidence limit. Since
the complex eq 19 simplifies to eq 20.

It is evident without curve fitting that and complex 2 shows a low
catalytic activity towards CEES oxidation. At high [CEES]
nearly all Au is present as Au(III), and eq 19 then simplifies to
eq 21 (details are in Boring, et al.) 22 :

Figure 4 shows saturation kinetics at [CEES] > 0.4M, which clearly
suggests that Thus, the CEES substrate slows the reaction by shifting
eq 8 to the right in favor of the less reactive 2 by substituting CEES for
and/or from the more reactive 1 . Eq 20 also demonstrates how sensitive
the overall reaction rate is to a change in and While the rate is linearly
proportional to the dependence on is more complex and varies with
and [CEES] as illustrated in Figures 3 and 4 by dashed and dotted
lines computed at different values of The effect of solvents and ligand
substitution on and is addressed below.
The dependence of the rate on Figure 3, was also fitted to eq
20, the solid curve is with and which are in
good agreement with those obtained from the fit of the rate vs. [CEES] data
and Surprisingly, our value for
is very similar to that for complexation of to in 5% aqueous
methanol: However, in the latter system is ~ 12. 27
While these two systems are very similar, they have different ligands (no
and more in the latter one) and solvent.