4.6 Article

Selective sulfoxidation of aryl sulfides by coordinatively unsaturated metal centers in chromium carboxylate MIL-101

Journal

APPLIED CATALYSIS A-GENERAL
Volume 358, Issue 2, Pages 249-253

Publisher

ELSEVIER
DOI: 10.1016/j.apcata.2009.02.018

Keywords

Metal-organic frameworks (MOFs); Sulfoxidation; Coordinatively unsaturated metal site (CUS); MIL-101; H2O2

Funding

  1. Korea Research Council for Industrial Science & Technology (ISTK)
  2. MOST/KOSEF [R11-2005-0008-00000-0]
  3. Seoul RBD Program [10816]
  4. CNRS

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The nanoporous chromium carboxylate MIL-101 with coordinatively unsaturated chromium sites has been shown to be active in the sulfoxidation of aryl sulfides with H2O2 to selectively produce the corresponding sulfoxides. Interestingly, the electron-releasing groups in the oxygenation reaction of para-X-phenylmethyl sulfoxides (X-Ph-S-CH3, X = CH3, H, NO2, and CN) enhanced the oxidation reactivity in 1:1 mixtures of X-Ph-S-CH3:H-Ph-S-CH3. Moreover, the O-18-labeled experiments to understand the source of oxygen in sulfoxide products proved that the oxygen atom in the sulfoxide product was entirely derived from H2O2. (C) 2009 Elsevier B.V. All rights reserved.

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