Biomimetic catalysis versus ligand activation: controlled process direction in reactions of PPh3 with [MO2(mnt)2]2- complexes (M = Mo, W)

This work focuses on the interaction of synthetic analogues of the molybdenum- and tungsten-containing oxotranferases' active sites [MO₂(mnt)₂]^2- (M = Mo or W, mnt - maleonitriledithiolate) with triphenylphosphine under both oxygen and inert atmospheres. Catalytic activity of these complexes in the oxidation of triphenylphosphine by oxygen was observed for the first time, with the tungsten complex exhibiting higher catalytic activity.

Additionally, in the case of the tungsten complex, activation of the coordinated mnt ligand was observed for the first time, leading to nucleophilic attack on a sulfur atom by triphenylphosphine with the triphenylphosphine sulfide formation. Thus, by changing the conditions of the process it is possible to control the direction of this reaction.