Chemical transformations of a SiO2-supported [Fe5RhC(CO)16]? cluster and catalysis of propylene hydroformylation |
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| Authors: | V I Koval'chuk N M Mikova A F Savitskii N V Chesnokov B N Kuznetsov |
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| Institution: | (1) Institute of the Chemistry of Natural Organic Materials, Russian Academy of Sciences, 42 ul. K. Marksa, 660049 Krasnoyarsk, Russian Federation;(2) Institute of Physics, Russian Academy of Sciences, Akademgorodok, 660036 Krasnoyarsk, Russian Federation |
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| Abstract: | Chemical transformations of SiO2-supported Fe5RhC(CO)16]– and Fe4RhC(CO)14]– clusters in Ar, CO, and synthesis gas are studied by IR spectroscopy, Mössbauer spectroscopy, and transmission electron microscopy. It is shown that partial transformation of the Fe5RhC(CO)16]– cluster to the Fe4RhC(CO)14]– cluster occurs immediately after its deposition on the substrate surface with the simultaneous formation of Fe2+ ions. The complete conversion of the supported Fe5RhC(CO)16]– cluster to Fe4RhC(CO)14]– is observed at 323 K in the synthesis gas. At 373 to 423 K Fe5RhC(CO)16]– transforms into a mixture of Fe4Rh2C(CO)16, Fe4RhC(CO)14]–, and Fe53Rh3C(CO)15]– clusters. In the 523 to 623 K range, the supported Fe5RhC(CO)16]– cluster decarbonylates completely to form bimetallic species Å 5 Å in size. Silica-supported FeRh clusters are active in propylene hydroformylation at 423 to 473 K and form a mixture of butyl alcohols and butyraldehydes.Translated fromIzvestiya Akademii Nauk. Seriya Khimicheskaya, No. 4, pp. 632–641, April, 1995.This work was financially supported by the Krasnoyarsk Region Scince Foundation (Grant No. 1F0020). |
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| Keywords: | carbonyl clusters silica gel propylene hydroformylation IR spectroscopy Mö ssbauer spectroscopy |
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