ETA(3)-ALLYL MOLYBDENUM DITHIOPHOSPHATE AND DITHIOPHOSPHINATE COMPLEXES WITH UNIDENTATE AND BIDENTATE NITROGEN DONOR LIGANDS - X-RAY STRUCTURE OF [MO-2(ETA(3)-C3H5)(2)(CO)(4)(S2P(OET)2)2(MU-NH2NH2)]

The bis(nitrile) complex [Mo(eta(3)-C3H5)(CO)(2)(NCMe)(2)Br] (1) reacts with ammonium diethyldithiophosphate or sodium diphenyldithiophosphinate to afford [Mo(eta(3)-C3H5)(Co)(2)(S(2)PX(2))(NCMe)] (2, X = OEt or Ph). The labile nitrile ligand in these complexes can be replaced by unidentate N-donors, L, affording mononuclear [Mo(eta(3)-C3H5)(CO)(2)(S(2)PX(2))(L)] (3, L = 4- NH(2)C(6)H(4)Me or py). Reactions of 2 with 0.5 equiv. of bidentate donors such as hydrazine or pyrazine produces binuclear complexes [Mo-2(eta(3) -C3H5)(2)(CO)(4)(S(2)PX(2))(2)(mu-N-N)] (4, N-N = N2H4 or pyrazine). An X-ray structure determination carried out on [Mo-2(eta(3)-C3H5)(2)(CO)(4){S2P(OEt)(2)}(2)(mu-NH2NH2)] (4a), showed the hydrazine bridge holding together two pseudo-octahedral 'Mo(eta(3)-C3H5)(CO)(2){S2P(OEt)(2)}(2)' fragments.