Summary
Rh6(CO)16 has been reacted with ≡Si−O−Si(OEt)3-n(CH2CH2PPh2)n (n = 1 or 3), together with their soluble mono- and tri- phosphine analogues, to form Rh6(CO)16−xPx (x ≃ 3) (P = PPh2CH2CH2Si≡), and with PPh3 to from the known compounds Rh6(CO)13(PPh3)3 and Rh6(CO)10(PPh3)6. Rh4(CO)12 reacts with (PPh2CH2CH2)2Si(OEt)2 to give Rh4(CO)10 (PPh2CH2CH2)2Si(OEt)2, a cluster that appears to change its structure upon reaction with silica. The supported molecular clusters obtained have a much higher thermal stability than those obtained when the clusters are simply adsorbed onto an untreated silica surface, although their catalytic activity for the hydrogenation of benzene indicates the formation of very small, metal particles also. Rh6(CO)13(PPh3)3, Rh6(CO)10(PPh3)6, Rh4(CO)10(PPh3)2, and Rh4(CO)10 (PPh2CH2CH2)2 Si(OEt)2 are active homogeneous catalysts, or catalyst precursors, for the hydrogenation of cyclohexene, but show only very slight activity for the hydrogenation of benzene.
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Smith, A.K. et al. (1979). Phosphine Substituted Rhodium Cluster Carbonyls in the Homogeneous and Supported Phases — Characterisation and Catalytic Activity. In: Tsutsui, M. (eds) Fundamental Research in Homogeneous Catalysis. Springer, Boston, MA. https://doi.org/10.1007/978-1-4613-2958-9_41
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