Bis(diphenylphosphino)methylamine as chelate ligand in pentamethylcyclopentadienylrhodium(III) and iridium(III) complexes.: Crystal structure of [(η<SUP>5</SUP>-C<sub>5</sub>Me<sub>5</sub>)RhCl(η<SUP>2</SUP>-<i>P,P</i>′-(PPh<sub>2</sub>)<sub>2</sub>NMe}]BF<sub>4</sub>
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2003
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Abstract
Reactions of the dimers [{(eta(5) -C5Me5)MCl(mu-Cl)}(2)] (M = Rh, Ir) with the ligand NMe(PPh2)(2) in 1:2 molar ratio afford the mononuclear cationic complexes [(eta(5)-C5Me5)MCl{eta(2)-P,P'-(Ph2P)(2)NMe}]Cl (M = Rh 1, Ir 2). Similar iodide complexes, [(eta(5)- C5Me5)MCl{eta(2)-P,P'-(Ph2P)(2)NMe}]I (M = Rh 3, Ir 4), can be prepared by N-functionalization of co-ordinated dppa ligand in complexes [(eta(5) -C5Me5)MCl{eta(2)-P,P'-(Ph2P)(2)NH}]BF4. The tetrafluoroborate derivatives, [(eta(5)-C5Me5)MCl{eta(2)-P,P'- (Ph2P)(2)NMe}]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 (H-1, P-31{H-1}) 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 coordination sphere. (C) 2002 Elsevier Science B.V. All rights reserved.
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rhodium, iridium, bis(diphenylphosphino)methylamine complexes, diphosphazane complexes, crystal structures