Oxygen atom transfer reaction involving oxomolybdenum complexes with sterically bulky thiocarboxylate ligands and biochemical interesting substrates in methanol at neutral pH

Abstract

Oxidation–reduction reactions of substrates in systems containing the complex [Mo VIO 2(O 2CC(S)CH 3Ph) 2] 2− in methanol have been investigated as models of oxo-transfer reactions. At neutral pH, the [Mo VIO 2(O 2CC(S)CH 3Ph) 2] 2− reacts with Me 2PhP or n-butanethiol to yield a [Mo IVO(O 2CC(S)CH 3Ph) 2] 2− species and Me 2PhPO or disulfide, respectively. The Mo IVO complex reduces a variety of substrates XO = Me 2SO and pyridine N-oxide conducing formation of X = Me 2S and pyridine. The occurrence of these reactions produces a catalytic system Me 2PhP + XO → Me 2PhPO + X and 2BuSH + XO → [BuS] 2 + X + H 2O. In this work we have also included the study of the reaction with biochemical interesting substrates, such as the reduction of nitrobenzene to aniline and catalytic air oxidation of benzoin to benzil.