CLUSTER CHEMISTRY LI. REACTIONS OF SOME SUBSTITUTED RUTHENIUM AND OSMIUM CLUSTER CARBONYLS WITH DIHYDROGEN. X-RAY CRYSTAL STRUCTURES OF Ru3(μ-H)2(μ3-PPh)(CO)8(PMePh2),Ru4(μ-H)4(μ-dppm)(CO)10, Ru4(μ-H)3(μ3-PPhCH2PPh2)(CO)10 AND Os3(μ-H)2(μ-dppm)(CO)8

Article abstract of DOI:10.1016/0022-328X(86)82088-5

The reaction of dihydrogen (80 deg C, 20bar, 2h) with a series of tertiary phosphine and phosphite complexes Ru3(CO)12-n(L)n (L=PMe3, PPh3' PPh (OMe)2 or P(OMe)3; n= 1-3), and with complexes containing dppm, dppe, dpam and PPh2(C6H4CH=CH2-2) have been studied.Complexes containing monodentate ligands gave tetranuclear complexes Ru4(μH)4(CO)12-n(L)n (n= 0-3, but not 4). whereas complexes with bidentate ligamnds showed varying behaviour.Thus Ru3(μ-dppm)(CO)10 gaveRu3(μ-H)2(μ3-PPhCH2PPh2)(CO)9, further hydrogenation of which afforded Ru3(μ-H)2(μ3-PPh)(CO)8(PMePh2).Ru3(μ-dppe)(CO)10 gave a mixture of Ru3(μ-H)(μ3-PPhCH2CH2PPh2)(CO)9 and Ru4(μ-H)4(μ-dppe)(CO)10 at the major products, and Ru3(μ-η ²,P-CH2=CHC6H4PPh2)(CO)10 gave a mixture of Ru4(μ-H)4(CO)12-nn (n=0 and 1).Pyrolysis of Ru4(μ-H)4(μ-dppm)(CO)10 afforded Ru4(μ--H)3(μ3-PPhCH2PPh2)(μ-CO)2(CO)8.The molecular structures of Ru3(μ-H)2(μ3-PPh))(CO)8(PMePh2), Ru4(μ-H)4(μ-dppm)(CO)10 and Ru4(μ-H)3(μ-PPhCH2PPh2)(μ-CO)2(CO)8 have been determined: 2286, 4930 and 6393 data (I=>2,5ρ(I)) were refined to R and R_w values of 0.032 and 0.037, 0.026 and 0.035 and 0.043 and 0.053, respectively.Hydrogenation of Os3(μ-dppm)(CO)10 gave Os3(μ-H)2(μ-dppm(CO)8, whose structure was also determined: 3367datawith I>=2.5ρ(I) were refined to R 0.044, R^w 0.052.