The reaction of Rh6(CO)16 at 25°C with a phosphinated silica surface, LSiO2, gives rise to the formation of zerovalent particles linked to the support, which have probably kept the Rh6 cluster frame. Their carbonylation leads to the formation of Rh6(CO)16 - x (LSiO2)x where x seems to be equal to 3 and from which the carbonyl ligands are not easily dissociated. Interaction at 80 °C of Rh6(CO)16 with the phosphinated silica support leads to the formation of a mixture of Rh(0) and Rh(I) species, which are interconvertible by oxidation or reduction, respectively, under mild conditions. The carbonyl species obtained show a much higher thermal stability than those obtained under similar conditions on pure silica surface.
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