Oxidation of primary benzylic amines by Mo(O) (O2)2(H2O)(HMPA)

The stoichiometric reactions of MO (O)(O2)2(H2O) (HMPA) (1) (HMPA = hexamethylphosphoramide) with primary benzylic amines, RNH2, [R=C6H5CH2 (2); 2,4Cl2-C6H3CH2 (3); 3,4(OCH3)2-C6H3CH2 (4); 2,Cl-C6H4CH2 (5)] yield the cis-dioxoperoxo complexes, Mo(O)2(O2)(RNH2)2,(2a-5a), the corresponding oximes, RCHNOH, and/or the Schiff bases, RCHNCH2R. The complex Mo(O)2(O2)(C6H5CH2NH2)2 (2a), obtained in the stoichiometric reaction of (1) with benzylamine, catalyzes the oxidation of (2) to benzaldehyde oxime, in the presence of H2O2 (30% w/w) as oxidant.