Oxidative addition reactions of triphenylphosphine with dodecacarbonyltriosmium

Abstract
Reaction of Os3(CO)12 with PPh3 in the mole ratio of 1 : 2 gave a mixture of nine products among which were the unusual new compounds HOs3(CO)9(PPh3)(PPh2C6H4), HOs3(CO)8(PPh3)(PPh2C6H4), HOs3(CO)7(PPh2)(PPh3)(C6H4), Os3(CO)8(PPh2)(Ph)(PPhC6H4), and Os3(CO)7(PPh2)2(C6H4). Decomposition of Os3(CO)10(PPh3)2 led to a similar mixture which also included the compound HOs3(CO)7(PPh2)(PPh2C6H4C6H3). Some analogous AsPh3 and P(C6H4Me)3 derivatives and the new protonated species [HOs3(CO)9(PPh3)3]+Br were also prepared, the latter to assist in n.m.r. studies. The general properties, structures, and i.r., high field n.m.r., and mass spectra of the new compounds are described.

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