Bis(diphenylphosphino)methylamine as chelate ligand in pentamethylcyclopentadienylrhodium(III) and iridium(III) complexes.: Crystal structure of [(η5-C5Me5)RhCl{η2-P,P′-(PPh2)2NMe}]BF4

Reactions of the dimers [{(η5-C5Me5)MCl(μ-Cl)}2] (M=Rh, Ir) with the ligand NMe(PPh2)2 in 1:2 molar ratio afford the mononuclear cationic complexes [(η5-C5Me5)MCl{η2-P,P′-(Ph2P)2NMe}]Cl (M=Rh 1, Ir 2). Similar iodide complexes, [(η5-C5Me5)MCl{η2-P,P′-(Ph2P)2NMe}]I (M=Rh 3, Ir 4), can be prepared by N-functionalization of co-ordinated dppa ligand in complexes [(η5-C5Me5)MCl{η2-P,P′-(Ph2P)2NH}]BF4. The tetrafluoroborate derivatives, [(η5-C5Me5)MCl{η2-P,P′-(Ph2P)2NMe}]BF4 (M=Rh 5, Ir 6) are prepared by reaction of complexes 1–4 with AgBF4 in acetone. All the compounds described are characterised by microanalysis, IR and NMR (1H, 31P{1H}) spectroscopy. The crystal structure of complex 5 is determined by X-ray diffraction methods. The complex exhibits a pseudo-octahedral molecular structure with a C5Me5 group occupying three co-ordination positions and a bidentate chelate P,P′-bonded ligand and a chloride atom completing the co-ordination sphere.