• gas-phase s-alkylation of benzenethiol with aliphatic alcohols, ethers, esters, alkyl halides and olefins over halide cluster catalysts of groups 5 and 6 transition metals

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    • تاریخ ارائه: 1392/07/24
    • تاریخ انتشار در تی پی بین: 1392/07/24
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     benzenethiol was reacted with methanol under a hydrogen stream over [(nb6cl12)cl2(h2o)4]·6h2o supported on silica gel. catalytic activity of the cluster commenced above 250 °c, yielding methyl phenyl sulfide. the selectivity was 98% at 400 °c. molybdenum, tantalum and tungsten halide clusters with the same octahedral metal framework also catalyzed the reaction. primary alcohols with shorter alkyl chains were effective reagents for the s-alkylation. aliphatic ethers, dialkyl carbonates, orthoesters and alkyl halides were effective reagents for the s-alkylation. when 1-hexene was applied to the reaction, spontaneous and catalytic s-alkylation proceeded simultaneously above 200 °c, yielding n-hexyl phenyl sulfide. when alkyl acetates were subjected to this reaction, the niobium cluster afforded s-phenyl thioacetate, and the other clusters afforded alkyl phenyl sulfides selectively. a brønsted acid site attributable to a hydroxo ligand, which is formed on the cluster complex by thermal activation, is proposed as the active site of the catalysts.

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