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Catalytic ring-opening addition of thiols to epoxides in the gas-phase over molecular rhenium sulfide cluster complexes [Re6S8X6] (X = Cl, OH, H2O) with retention of their octahedral metal frameworks

Paper ID Volume ID Publish Year Pages File Format Full-Text
39286 45816 2015 9 PDF Available
Title
Catalytic ring-opening addition of thiols to epoxides in the gas-phase over molecular rhenium sulfide cluster complexes [Re6S8X6] (X = Cl, OH, H2O) with retention of their octahedral metal frameworks
Abstract

•Aliphatic and aromatic thiols added to epoxides to yield β-hydroxy sulfides.•The selective gas-phase catalysis proceeded at 175–250 °C.•Molecular rhenium sulfide clusters catalyzed the reaction.•The activation mechanism of rhenium cluster was investigated.•Brønsted acid sites developed on the rhenium cluster.

A series of molecular rhenium sulfide clusters K4[Re6S8Cl6] (1), K4[Re6S8(OH)6], and [Re6S8(H2O)6]SO4 supported on silica gel catalyze ring-opening addition of thiols to epoxides to yield β-hydroxy sulfides in a stream of hydrogen at temperatures ranging from 175 to 250 °C. The thermal activation mechanisms of 1 is studied. Powder X-ray diffraction analyses and Raman spectrometry reveal the retention of integrity of the octahedral cluster framework up to 500 °C. Thermogravimetry and elemental analyses of the silica gel-supported 1 show the loss of chlorido ligands, and evolution of hydrogen chloride is observed on activation. No coordinatively unsaturated metal site is observed by CO titration. Titration of the activated cluster shows the appearance of weak Brønsted acid sites with H0 ≈ 1.8. The catalytically active site of the silica gel-supported 1 is a hydroxo ligand that is formed by reaction with silanol groups.

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Keywords
Rhenium sulfide cluster; Chlorido ligand; Brønsted acid; Thiol; Epoxide
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Catalytic ring-opening addition of thiols to epoxides in the gas-phase over molecular rhenium sulfide cluster complexes [Re6S8X6] (X = Cl, OH, H2O) with retention of their octahedral metal frameworks
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Publisher
Database: Elsevier - ScienceDirect
Journal: Applied Catalysis A: General - Volume 497, May 2015, Pages 167–175
Authors
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Subjects
Physical Sciences and Engineering Chemical Engineering Catalysis
Get Full-Text Now
Don't Miss Today's Special Offer
Price was $35.95
You save - $31
Price after discount Only $4.95
100% Money Back Guarantee
Full-text PDF Download
Online Support
Any Questions? feel free to contact us