Complexation and metallation of Ph 2PC [tbnd]C(CH 2) 5C [tbnd]CPh 2 in triosmium carbonyl clusters

Abstract

Reaction of Ph 2PC C(CH 2) 5C CPh 2 with Os 3(CO) 10(NCMe) 2 affords Os 3(CO) 10(μ,η 2-(Ph 2P) 2C 9H 10) ( 1) and the double cluster [Os 3(CO) 10] 2(μ,η 2- (Ph 2P) 2C 9H 10) 2 ( 2), through coordination of the phosphine groups. Thermolysis of 1 in toluene generates Os 3(CO) 7(μ-PPh 2)(μ 3,η 5-Ph 2PC 9H 10) ( 3) and Os 3(CO) 8(μ-PPh 2)(μ 3,η 6-Ph 2P(C 9H 10)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.