Complexation and metallation of Ph2PCtriple bond; length of mdashC(CH2)5Ctriple bond; length of mdashCPh2 in triosmium carbonyl clusters

Reaction of Ph2PCtriple bond; length of mdashC(CH2)5Ctriple bond; length of mdashCPh2 with Os3(CO)10(NCMe)2 affords Os3(CO)10(μ,η2-(Ph2P)2C9H10) (1) and the double cluster [Os3(CO)10]2(μ,η2- (Ph2P)2C9H10)2 (2), through coordination of the phosphine groups. Thermolysis of 1 in toluene generates Os3(CO)7(μ-PPh2)(μ3,η5-Ph2PC9H10) (3) and Os3(CO)8(μ-PPh2)(μ3,η6-Ph2P(C9H10)CO) (4). The molecular structures of 1, 3, and 4 have been determined by an X-ray diffraction study. Both 3 and 4 contain a bridging phosphido group and a carbocycle connected to an osmacyclopentadienyl ring, which are apparently derived from C–P bond activation and C–C bond rearrangement of the dpndy ligand governed by the triosmium clusters.