Organodioxygen Complexes of Lanthanides and their Oxygen Transfer Reactions

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Several organodioxygen complexes of lanthanum(lII) and cerium(IV) have been synthesized using different type of ligands. These complexes had the compositions, [La(O2)(det)(NO3)2] (1). [La(O2) (tet) (NO3)2] (2). [La(O2)(C5H5N),NO3](3)[La(O2)(C6H18N3PO)2] (4) [La(O2) (OPPh3)2(NO3)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 reveal that (3) is a peroxo complex while the other complexes are superoxo type, in particular. The IR spectrum of (3) gives n1(O-O) at 851cm-1 while the Raman spectra of (4), (5), (7) and (8) give n1(O2) bands at 1046 cm-1, 1032cm-1, 1100cm-1 and 1046cm-1, respectively. The oxygen transfer reactions of two selected complexes were carried out under stoichiometric conditions. The complex containing 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

organodioxygen lanthanum; synthesized; tridentate ligand