Benzenethiol was reacted with methanol under a hydrogen stream over [(Nb6Cl12))Cl-2(H2O)(4)]center dot 6H(2)O supported on silica gel. Catalytic activity of the cluster commenced above 250 degrees 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 degrees 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 Bronsted 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. (C) 2012 Elsevier B.V. All rights reserved.