A biomimetic phenol substituent effect on the reaction of a dimethylplatinum(ii) complex with oxygen: proton coupled electron transfer and multiple proton relay.

The complex [PtMe2({κ(2)-N,N-RN[double bond, length as m-dash]CH-2-C5H4N})] reacts with oxygen in acetone solution to give the platinum(iv) complex [Pt(OH)Me2{κ(3)-N,N,O-RNH-CH(2-C5H4N)(CH[double bond, length as m-dash]CMeO)}], when R = 2-C6H4OH, but not when R = Ph. It has been suggested that the phenol substituent plays two key biomimetic roles; firstly, in proton coupled electron transfer reactions in the activation of oxygen and hydroperoxide groups and, secondly, in proton relay from a methyl group of the coordinated acetone.