Cluster chemistry LXIII. Further studies of the thermal behaviour of 2(μ-dppa) (dppa = C2(PPh2)2). Crystal structures of Ru4(μ4-PPh)(μ4-PhC2PPh2)(μ-CO)2(CO)8*MeOH, Ru5(μ4-PPh)3-CCPh(PPh2)>(CO)12, Ru5(μ3-H)(μ4-PPh)4-CCPh(C6H4)>(μ3-PPh)(CO)10 and

Article abstract of DOI:10.1016/0022-328X(90)80158-V

Large scale (ca. 2 g) preparations of Ru5(μ5-C2PPh2)(μ-PPh2)(CO)13 (2) by pyrolysis of 2(μ-dppa) have also afforded the complexes Ru4(μ₄-PPh)(μ₄-PhC2PPh2)(μ-CO)2(CO)8 (3), Ru5(μ-C2PPh2)(μ-PPh2)(CO)15 (4t), Ru4(μ₄-C2)(μ-PPh2)2(CO)12 (5), Ru5(μ₄-PPh)<μ₃-CCPh(PPh2)>(CO)12 (6) and Ru5(μ-H)(μ₄-PPh)<μ₄-CCPh(C6H4)>(μ₃-PPh)(CO)10 (7).The new complexes 6 and 7, identified crystallographically, are formed by heating 2; the evolved CO reacts with 2 to give 4t and 7.Complex 6 contains a square pyramidal Ru5 core, the square face being capped by PPh, and a triangular face by the phosphino-vinylidene ligand, which is formed by migration of Ph from P to C_β of the C2PPh2 ligand in 2.Complex 7 contains a CPRu5 pentagonal bipyramid, with PPh capping an Ru3 face.Complex 7 reacts with MeOH to give Ru5(μ₄-PPh)<μ₄-CCPh(C6H4)><μ-PPh(OMe)>(CO)11 (12), with the same core as 7; the μ₃-PPh group has been converted to a μ-phosphido ligand.In 7 and 12, the organic fragment is a metallated diphenylvinylidene.Some 31P NMR data for these and related complexes are given and discussed.The crystal structure of 3 as its methanol solvate is also reported.