Cationic molybdenum complexes with P-coordinated (diphenylphosphino)alkynes

New cationic P-coordinated (diphenylphosphino)alkyne complexes with molybdenum [(Mp)Ph2PCCR][BF4] {R=H, Me, tBu, Ph, Tol; Mp=(C5H5)Mo(CO)3} have been prepared from reaction between a (diphenylphosphino)alkyne Ph2PCCR and the dinuclear complex [(C5H5)Mo(CO)3]2, with Ag(I) as oxidant. The bis(diphenyphosphosphino)acetylene Ph2PCCPPh2 led to the following homo- and heteronuclear metal complexes by the same method: [(Mp)Ph2PCCPPh2][BF4], [(Mp)Ph2PCCPPh2(Mp)][BF4]2 and [(Mp)Ph2PCCPPh2(Fp)][BF4]2 {Fp=(C5H5)Fe(CO)2}. The reaction of the P-coordinated molybdenum complexes [(Mp)Ph2PCCR][BF4] with dicobalt octacarbonyl at room temperature afforded the cationic heterometallic complexes [(Mp)Ph2PC2R{Co2(CO)6}][BF4]. All complexes were characterised by microanalysis and IR, 1H-, 13C- and 31P-NMR spectroscopy.