Five Co-ordinate Complexes of Platinum(II) and Palladium(II)

Reactions of 1,10-phenanthroline with halogen bridged dinuclear species, [M2X2(PPh2O)2(PPh2OH)2] and [M2X2(PR3)4][BF4]2, give the new five co-ordinate complexes, [MX(PPh2O)(PPh2OH)(Phen)] and [MX(PR3)2(Phen)][BF4], where M = Pd or Pt, X = Cl or Br, Ph = phenyl, and R = ethyl (or phenyl when M = Pd). Decomposition of the [MX(PR3)2(Phen)][BF4] complexes in hot solvents gives the four co-ordinate species, [MX(PR3)(Phen)][BF4]. The complexes are characterized by elemental analyses, molecular weight, and conductance measurements and infrared and nuclear magnetic resonance spectroscopy. The spectroscopic data show that [PtCl(PEt3)2(Phen)][BF4] has a trigonal bipyramidal structure with the phenanthroline and one triethylphosphine in the equatorial plane and a chlorine and a triethylphosphine in the axial positions.