Di- and tri-nuclear molybdenum-palladium complexes bearing strong π-acceptor "P-N-P" ligands, MeN{P(OR)2}2 (R = CH2CF3 or Ph)

Ganesan, Mani ; Krishnamurthy, Setharampattu S. ; Nethaji, Munirathinam (2005) Di- and tri-nuclear molybdenum-palladium complexes bearing strong π-acceptor "P-N-P" ligands, MeN{P(OR)2}2 (R = CH2CF3 or Ph) Journal of Organometallic Chemistry, 690 (4). pp. 1080-1091. ISSN 0022-328X

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Official URL: http://linkinghub.elsevier.com/retrieve/pii/S00223...

Related URL: http://dx.doi.org/10.1016/j.jorganchem.2004.10.053

Abstract

The dipalladium complexes, [PdCl(μ-MeN{P(OR)2}2)]2 (R = CH2CF3, 1a; Ph, 1b) react with [Mo25-C5H5)2(CO)6] in boiling benzene to afford the molybdenum-palladium heterometallic complexes, [(η5-C5H5)(CO)Mo(μ-MeN{P(OR)2}2)2PdCl] (R = CH2CF3, 3a; Ph, 3b), [(η5-C5H5)Mo(μ3-CO)2(μ-MeN{P(OR) 2}2)2Pd2Cl], (R = CH2CF3, 5a; Ph, 5b), [(η5-C5H5)(Cl)Mo(μ2-CO)(μ 2-Cl)(μ-MeN{P(OR)2}2)PdCl], (R = CH2CF3, 6a; Ph, 6b) and also the mononuclear complex [Mo(CO)Cl(η5-C5H5)(κ2-MeN{P(OR)2}2)], (R = Ph, 4b). These complexes have been separated by column chromatography and are characterised by elemental analysis, IR, 1H, 31P{1H} NMR data. The structures of 1a, 3a, 4b, 5b and 6a have been confirmed by single crystal X-ray diffraction. The CO ligands in 5b and 6a adopt a semi-bridging mode of bonding; the Mo-CO distances (1.95-1.97 Å) are shorter than the Pd-CO distances (2.40-2.48 Å). The Pd-Mo distances fall in the range, 2.63-2.86 À. The reaction of [Mo25-C5H5)2(CO)6] with MeN{P(OPh)2}2 in toluene gives [Mo2(CO)45-C5H5)21-MeN{P(OPh)2}2)2] (2) in which the diphosphazane acts as a monodentate ligand.

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