{"status":"ok","message-type":"work","message-version":"1.0.0","message":{"indexed":{"date-parts":[[2026,4,3]],"date-time":"2026-04-03T16:26:04Z","timestamp":1775233564681,"version":"3.50.1"},"reference-count":82,"publisher":"Wiley","issue":"18","license":[{"start":{"date-parts":[[2003,9,11]],"date-time":"2003-09-11T00:00:00Z","timestamp":1063238400000},"content-version":"vor","delay-in-days":0,"URL":"http:\/\/onlinelibrary.wiley.com\/termsAndConditions#vor"}],"content-domain":{"domain":[],"crossmark-restriction":false},"short-container-title":["Chemistry A European J"],"published-print":{"date-parts":[[2003,9,22]]},"abstract":"<jats:title>Abstract<\/jats:title><jats:p>Mo <jats:italic>K<\/jats:italic>\u2010edge XAFS spectra have been measured for ordered mesoporous silica MCM\u201041 grafted with the complexes [MoO<jats:sub>2<\/jats:sub>X<jats:sub>2<\/jats:sub>(thf)<jats:sub>2<\/jats:sub>] (X=Cl, Br). For grafting reactions in the absence of triethylamine, materials with 1 wt.\u2009% Mo are obtained; the Mo <jats:italic>K<\/jats:italic>\u2010edge EXAFS results indicate the co\u2010existence of isolated surface\u2010fixed monomeric species {MoO<jats:sub>2<\/jats:sub>[(\uf8ffO)<jats:sub>3<\/jats:sub>SiO]<jats:sub>2<\/jats:sub>(thf)<jats:sub><jats:italic>n<\/jats:italic><\/jats:sub>} and {MoO<jats:sub>2<\/jats:sub>[(\uf8ffO)<jats:sub>3<\/jats:sub>SiO]X(thf)<jats:sub><jats:italic>n<\/jats:italic><\/jats:sub>}. When Et<jats:sub>3<\/jats:sub>N is used in the grafting reactions, materials with 4 wt.\u2009% Mo are obtained. The EXAFS data for the material prepared using [MoO<jats:sub>2<\/jats:sub>Cl<jats:sub>2<\/jats:sub>(thf)<jats:sub>2<\/jats:sub>] and Et<jats:sub>3<\/jats:sub>N indicate the presence of dinuclear species with two Mo<jats:sup>VI<\/jats:sup> centres, each with two Mo\uf8feO groups and each linked by one or two oxo bridges (Mo<jats:bold>\u22c5\u22c5\u22c5<\/jats:bold>Mo 3.27 \u00c5). The molybdenum centres in the material prepared using the dibromo complex comprise mainly isolated four\u2010coordinate dioxomolybdenum(<jats:sc>VI<\/jats:sc>) and trioxomolybdenum(<jats:sc>VI<\/jats:sc>) monomeric species, with a small contribution from dimeric species. All materials were further characterised in the solid state by powder X\u2010ray diffraction, N<jats:sub>2<\/jats:sub> adsorption analysis, MAS NMR (<jats:sup>13<\/jats:sup>C, <jats:sup>29<\/jats:sup>Si) and FTIR spectroscopy. The derivatised MCMs perform differently as catalysts in the liquid\u2010phase oxidation of various olefins and alcohols with <jats:italic>tert<\/jats:italic>\u2010butyl hydroperoxide. The highest alkene epoxidation activity was recorded for the catalysts with low metal loading, whereas the material containing oxo\u2010bridged dimers had the highest activity for oxidation of alcohols. The recyclability of all the catalysts was tested: the catalytic activity of the derivatised materials tended to stabilize with ageing.<\/jats:p>","DOI":"10.1002\/chem.200304887","type":"journal-article","created":{"date-parts":[[2003,9,17]],"date-time":"2003-09-17T10:19:45Z","timestamp":1063793985000},"page":"4380-4390","source":"Crossref","is-referenced-by-count":62,"title":["Molecular Structure\u2013Activity Relationships for the Oxidation of Organic Compounds Using Mesoporous Silica Catalysts Derivatised with Bis(halogeno)dioxomolybdenum(<scp>VI<\/scp>) Complexes"],"prefix":"10.1002","volume":"9","author":[{"given":"Carla D.","family":"Nunes","sequence":"first","affiliation":[]},{"given":"Anabela A.","family":"Valente","sequence":"additional","affiliation":[]},{"given":"Martyn","family":"Pillinger","sequence":"additional","affiliation":[]},{"given":"Jo\u00e3o","family":"Rocha","sequence":"additional","affiliation":[]},{"given":"Isabel 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