Organodioxygen complexes of some heavy metal ions and their oxygen transfer reactions

Several novel organodioxygen complexes of lanthanide ions, viz., lanthanum(m) and cerium(IV) have been synthesized containing a number of organic co- ligands. The complexes characterized were, [La(02)(det)(N03)2] (1), [La(O2)(tet)(NO3)2] (2), [La(O2)(C5H5N)2NO3] (3), [La(O2)(C6H18N3PO)2(NO3)2] (4), [La(02)(OPPh3)2(N03)2] (5), [La(O2)2(NH2CH2CH2NH2)2NO3] (6), [La(O2)(PPh3)2(NO3)2] (7) and [Ce(O2)(C6H18N3PO)2(NO3)3] (8). IR and Raman spectra revealed that (3) was a peroxo complex while the others were, in particular, superoxo type. The IR spectrum of (3) gives V1(O-O) at 851 cm-1 while the Raman spectra of (4), (5), (7) and (8) give V1(O2) bands at 1046 cm-1, 1032 cm1, 1100 cm-1 and 1046 cm-1, respectively. The oxygen transfer reactions of two selected complexes were carried out under stoichiometric conditions. The complex containing a bidentate ligand, (6), was found to oxidize triphenylphosphine and trans-stilbene to their oxides while the complex containing tridentate ligand (1) was stable and inert towards oxidation. (author)