OXIDATION OF PRIMARY BENZYLIC AMINES BY MO(O)(O2)2(H2O)(HMPA)

The stoichiometric reactions Of Mo(O)(O2)2(H2O) (HMPA) (1) (HMPA = hexamethyl-phosphoramide) 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, RCH=NOH, and/or the Schiff bases, RCH=NCH2R. 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.