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  • Thursday, January 28, 1993
  • Cluster vs. non-cluster catalysis in olefin thermal hydrosilylation and isomerization reactions using Ru3(CO)12
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  • H. S. Hilal*, Shukri Khalaf and Waheed Jondi,J. Organometal. Chem., 452( 1993)167-173



    The ruthenium cluster Ru$CO)~~ (1) has been evaluated as a catalyst precursor for the thermal reactions of l-octene with

    (EtO),SiH in a mixture of dioxane and benzene at temperatures of 50-75°C. At 70°C or higher, olefin isomerization and

    hydrosilylation reactions were observed; the products,

    tram-Zoctene and CsHIICH2CHZCH,Si(OEt), (2) were identified. The

    reactions were accompanied by a side reaction that involved generation of hydrogen gas. The sum of the rates of appearance of 2

    and H, equalled the rate of disappearance of (EtO),SiH. No significant isomerization was observed in the absence of (EtO),SiH.

    Maximum turnover number values of 7.50, 70, and 70 were obtained for isomerization, hydrosilylation, and H, production

    reactions, respectively. At WC or lower, no hydrosilylation or hydrogen production was observed, and the only product was

    trans-2-octene. No detectable disappearance of (EtO),SiH was observed. Acetophenone was also hydrosilated by use of cluster


    as catalyst; the only product obtained was (EtO),SiOC(PhXHXCH,). Kinetic studies indicated that the reactions of 1-octene and

    the reaction of acetophenone involved a catalytically active species of lower nuclearity. There was evidence of concurrent cluster

    catalysis, especially during the first few minutes of the reaction.

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Hikmat S. Hilal
Organometallics (organic and inorganic), Materials, Catalysis, Semiconductors, Photoelectro-chemistry
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