Direct oxygen atom transfer versus electron transfer mechanisms in the phosphine oxidation by nonheme Mn(IV)-oxo complexes

Abstract

Direct oxygen atom transfer from a nonheme Mn(iv)-oxo complex, [(Bn-TPEN)MnIV(O)]2+, to triphenylphosphine (Ph3P) derivatives occurs with a significant steric effect resulting from the ortho-substituents on the phenyl group of the Ph3P derivatives, whereas the phosphine oxygenation by a Mn(iv)-oxo complex in the presence of HOTf occurs via an electron transfer mechanism without the substrate-steric effect. © 2017 The Royal Society of Chemistry.