Oxygen atom transfer reaction involving oxomolybdenum complexes with sterically bulky thiocarboxylate ligands and biochemical interesting substrates in methanol at neutral pH
摘要:
Oxidation-reduction reactions of substrates in systems containing the complex [(MoO2)-O-VI(O2CC(S)CH3Ph)(2)](2-) in methanol have been investigated as models of ore-transfer reactions. At neutral pH, the [(MoO2)-O-VI(O2CC(S)CH3Ph)(2)](2-) reacts with Me2PhP or n-butanethiol to yield a [(MoO)-O-IV(O2CC(S)CH3Ph)(2)](2-) species and Me2PhPO or disulfide, respectively The (MoO)-O-IV complex reduces a variety of substrates XO = Me2SO and pyridine N-oxide conducing formation of X = Me2S and pyridine. The occurrence of these reactions produces a catalytic system Me2PhP + XO --> Me2PhPO + X and 2BuSH + XO --> [BuS](2) + X + H2O. 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. (C) 1999 Elsevier Science S.A. All rights reserved.