CLUSTER CHEMISTRY. XXXVIII. REACTIONS BETWEEN M(C2R)(PR'3) (M=Cu, Ag. Au; R=Ph, C6F5; R'=Me, Ph) AND H2OS3(CO)10: X-RAY STRUCTURES OF Os3Au(μ-CH=CHR)(CO)10(PPh3) (R=Ph AND C6F5)

Article abstract of DOI:10.1016/0022-328X(85)88013-X

The reactions of Os3(μ-H)(CO)10 with a series of Group IB metal acetylide-tertiary phosphine complexes are described.Whereas the compounds M(C2C6F5)(PPh3) (M=Cu, Ag, Au) afforded the complexes MOs3(μ-CH=CHC6Fpercent)(CO)10(PPh3) cleanly and in high yield, complex mixtures of products were obtained from reactions of the analogous phenylacetylides.The complexes MOs3(μ-H)(CO)10(PPh3), MOs3(μ-CH=CHPh)(CO)9(PPh3)2 and MOs3(μ-H9(CO)10(PPh3) (of known structure), and MOs3(μ-CH=CHPh)(CO)9(PPh3)2 and HMOs3(CH=CPh)(CO)8 (of known structure) were characterised; Au(C2Ph)(PMe3) afforded similar derivatives.The reactions proceed by oxidative-addition and hydrogen migration steps; M-P bond cleavage reactions also occur to a small extent.The molecular structures of AuOs3(μ-CH=CHC6R5)(CO)10(PPh3) (R=F or H) were determined by X-ray analyses.For R=F, crystals are triclinic, space group P<*>, with a 9.081(2), b 13.291(2), c 17.1419(2) Angstroem, α 84.49(1), β 76.20(2), γ 75.81(2) deg and Z=2< 4622 observed data 2.5?(I)> were refined to R=0.027, R_w=0.031.For R=H, crzstals are triclinic, space group P<*>, with a 9.403(4), b13.448(3), c 13.774(4) Angstroem, α 83.34(2), β 88.66(3), γ 70.21(3) deg, and Z=2; 4405 observed data 2.5?(I)> were refined to R=0.030, R_w=0.033.The two molecules differ in the orientation of the Ph rings of the PPh3 groups, but are otherwise similar to Os3(μ-H)(μ-CH=CHBu^t)(CO)10 with the μ-H ligand replaced by the isolobal μ-Au(PPh3) group.