PREPARATION AND STRUCTURAL CHARACTERIZATION OF RHODIUM AND PALLADIUM COMPLEXES OF MIXED PHOSPHINE AMINE LIGANDS WITH METHYLENE SPACERS BETWEEN DONOR ATOMS

The condensation of paraformaldehyde with diphenylphosphine and diphenylamine yields Ph2- PCH2NPh2 (1), with diphenylphosphine and aniline yields Ph2PCH2N(Ph)CH2PPh2 (3), with phenylphosphine and diphenyl amine yields Ph2NCH2P(Ph)NPh2 (2) and with diphenylphosphine and ethylenediamine yields (Ph2PCH2)2N(CH2)2N(CH2- PPh2)2 (4). Reactions of 1 and 2 with Rh2(CO)4(μ- Cl)2 yield yellow Rh(Ph2PCH2NPh2)2(CO)Cl (5) and Rh{(Ph2NCH2)2PPh}2(CO)Cl (6), respectively. X-ray diffraction studies show that these have planar RhP2(CO)Cl cores with the nitrogen atoms uncoordinated. Reactions of 3 and 4 with (PhCN)2PdCl2 yields complexes with bidentate P,P chelate rings. The X-ray crystal structures of Pd{(Ph2PCH2)2NPh}Cl2 and Pd2{(Ph2PCH2)2NCH2}2I4 are reported. In the latter the two planar PdP2I4 coordination units are widely separated (Pd...Pd, 10.197(1) Å). © 1990.