HOMO-DINUCLEAR AND HETERO-DINUCLEAR COMPLEXES OF PALLADIUM AND PLATINUM-CONTAINING PHOSPHINOACETYLENE AND/OR CHLORIDE AS BRIDGING LIGANDS

Reactions between the diphenylacetylenephosphine complexes cis-[M'Cl-2(PPh(2)C=CR)(2)] (M' = Pt or Pd, R = Ph or Bu(t)) and cis-[M(C6F5)(2)(thf)(2)] (M = Pt or Pd; thf = tetrahydrofuran) in a 1:1 molar ratio have been studied. Three types of products have been obtained: (a) asymmetric homo- and hetero-dinuclear complexes gem-[(C6F5)(2)M(mu-Cl)(2)M'(PPh(2)C=CR)(2)], (b) symmetric trans-palladium derivatives [{Pd(mu-Cl)(C6F5)(PPh(2)C=CR)}(2)] and (c) the unusual chloride and diphenyl (phenylethynyl) phosphine bridged dinuclear compounds [(C6F5)(2)Pt(mu-Cl)(mu-PPh(2)C=CPh)M'Cl(PPh(2)C=CPh)]. The complexes have been characterised by microanalysis. IR and NMR spectroscopy and the molecular structure of [(C6F5)(2)Pt(mu-Cl)(mu-PPh(2)C=CPh)PtCl(PPh(2)C=CPh)]. OC4H8. The NMR spectral data (H-1, F-19 and P-31) indicate that, in solution, mixtures of isomers [(C6F5)(2)Pt(mu-Cl)(2)M'(PPh(2)C=CR)(2)] and [(C6F5)(2)Pt(mu-Cl)(mu-PPh(2)C=CPh)M'Cl(PPh(2)C=CPh)] are present.