Synthesis, characterisation, and reactivity of transition metal carbonyl clusters containing an interstitial phosphorus in a trigonal co-ordination environment: the X-ray structures of [PPh3Me][Os6(CO)18P] and [Os6(CO)18P(AuPPh3)]

Abstract

Thermolysis of [Os₆H₂(CO)₂₁(PH)](1) or [Os₆H(CO)₂₁(PH)]^–(2) results in the closing up of the cluster framework to afford the interstitial phosphide clusters [Os₆H(CO)₁₈P](3) and [Os₆H(CO)₁₈P]^–(4), respectively; treatment of (3) with X^–(X = Cl, Br) also gives the anion (4), while both (3) and (4) react with [AuPPh₃]⁺ to yield [Os₆(CO)₁₈P(AuPPh₃)](6); X-ray analyses of (4) and (6) show that they contain a phosphide-centred trigonal prismatic metallic core.