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The grafted material (3.3 wt.\u2010% Mo) was tested as a catalyst for the epoxidation of cyclooctene with <jats:italic>tert<\/jats:italic>\u2010butyl hydroperoxide (TBHP) at 55 \u00b0C. Selectivity to the epoxide was very high and the observed kinetic profile was similar to that of the complex [MoO<jats:sub>2<\/jats:sub>Cl<jats:sub>2<\/jats:sub>(L\u2010L)] in the homogeneous phase. On recycling several times, some activity was lost from the first to second runs, but thereafter stabilised. Tethered complexes of this type were also prepared by a stepwise approach. The mesoporous silicas MCM\u201041 and MCM\u201048 were first treated with a toluene solution of the ligand L\u2010L under reflux. Before isolating the grafted materials, the silylating agent Me<jats:sub>3<\/jats:sub>SiCl was added to remove the residual Si\u2212OH groups on the surface of the mesoporous materials. Oxomolybdenum species were subsequently introduced into the ligand\u2010silicas by pore volume impregnation of a solution of the complex [MoO<jats:sub>2<\/jats:sub>Cl<jats:sub>2<\/jats:sub>(THF)<jats:sub>2<\/jats:sub>] in CH<jats:sub>2<\/jats:sub>Cl<jats:sub>2<\/jats:sub> at room temperature. The modified materials have been characterised by powder X\u2010ray diffraction, N<jats:sub>2<\/jats:sub> adsorption, and solid\u2010state MAS NMR (<jats:sup>13<\/jats:sup>C, <jats:sup>29<\/jats:sup>Si). Despite having lower metal loadings (1 wt.\u2010% Mo), the materials exhibited similar catalytic activities for the epoxidation of cyclooctene to that of the modified MCM\u201041 with 3.3 wt.\u2010% of Mo. However, selectivities to the epoxide were lower. The MCM supported catalysts have also been tested for the epoxidation of cyclododecene and \u03b1\u2010pinene with TBHP. (\u00a9 Wiley\u2010VCH Verlag GmbH &amp; Co. KGaA, 69451 Weinheim, Germany, 2003)<\/jats:p>","DOI":"10.1002\/ejic.200300278","type":"journal-article","created":{"date-parts":[[2003,10,28]],"date-time":"2003-10-28T08:00:39Z","timestamp":1067328039000},"page":"3870-3877","update-policy":"https:\/\/doi.org\/10.1002\/crossmark_policy","source":"Crossref","is-referenced-by-count":46,"title":["Dioxomolybdenum(<scp>VI<\/scp>)\u2010Modified Mesoporous MCM\u201041 and MCM\u201048 Materials for the Catalytic Epoxidation of Olefins"],"prefix":"10.1002","volume":"2003","author":[{"given":"Carla\u00a0D.","family":"Nunes","sequence":"first","affiliation":[]},{"given":"Martyn","family":"Pillinger","sequence":"additional","affiliation":[]},{"given":"Anabela\u00a0A.","family":"Valente","sequence":"additional","affiliation":[]},{"given":"Jo\u00e3o","family":"Rocha","sequence":"additional","affiliation":[]},{"given":"Andr\u00e9\u00a0D.","family":"Lopes","sequence":"additional","affiliation":[]},{"given":"Isabel\u00a0S.","family":"Gon\u00e7alves","sequence":"additional","affiliation":[]}],"member":"311","published-online":{"date-parts":[[2003,10,28]]},"reference":[{"key":"e_1_2_6_1_2","unstructured":"\u00a0"},{"key":"e_1_2_6_2_2","doi-asserted-by":"publisher","DOI":"10.1021\/cr00093a001"},{"key":"e_1_2_6_3_2","doi-asserted-by":"publisher","DOI":"10.1021\/cr00027a002"},{"key":"e_1_2_6_4_2","doi-asserted-by":"publisher","DOI":"10.1021\/cr9703212"},{"key":"e_1_2_6_5_2","doi-asserted-by":"publisher","DOI":"10.1021\/cr010333u"},{"key":"e_1_2_6_6_2","unstructured":"\u00a0"},{"key":"e_1_2_6_7_2","doi-asserted-by":"publisher","DOI":"10.1002\/cber.19941271206"},{"key":"e_1_2_6_8_2","doi-asserted-by":"publisher","DOI":"10.1016\/1381-1169(95)00099-2"},{"key":"e_1_2_6_9_2","doi-asserted-by":"publisher","DOI":"10.1002\/anie.199517371"},{"key":"e_1_2_6_10_2","doi-asserted-by":"publisher","DOI":"10.1002\/chem.19970030508"},{"key":"e_1_2_6_11_2","doi-asserted-by":"publisher","DOI":"10.1016\/S0022-328X(99)00102-3"},{"key":"e_1_2_6_12_2","doi-asserted-by":"publisher","DOI":"10.1016\/S1381-1169(99)00262-9"},{"key":"e_1_2_6_13_2","doi-asserted-by":"publisher","DOI":"10.1016\/S1381-1169(00)00200-4"},{"key":"e_1_2_6_14_2","unstructured":"\u00a0"},{"key":"e_1_2_6_15_2","doi-asserted-by":"publisher","DOI":"10.1002\/(SICI)1099-0682(200005)2000:5<1107::AID-EJIC1107>3.0.CO;2-E"},{"key":"e_1_2_6_16_2","doi-asserted-by":"publisher","DOI":"10.1002\/1521-3765(20020517)8:10<2370::AID-CHEM2370>3.0.CO;2-A"},{"key":"e_1_2_6_17_2","doi-asserted-by":"publisher","DOI":"10.1021\/cr010368u"},{"key":"e_1_2_6_18_2","unstructured":"\u00a0"},{"key":"e_1_2_6_19_2","doi-asserted-by":"publisher","DOI":"10.1016\/S0920-5861(99)00311-9"},{"key":"e_1_2_6_20_2","doi-asserted-by":"publisher","DOI":"10.1006\/jcat.1999.2399"},{"key":"e_1_2_6_21_2","doi-asserted-by":"publisher","DOI":"10.1006\/jcat.1995.1091"},{"key":"e_1_2_6_22_2","doi-asserted-by":"publisher","DOI":"10.1006\/jcat.1995.1092"},{"key":"e_1_2_6_23_2","doi-asserted-by":"publisher","DOI":"10.1016\/1381-1169(95)00224-3"},{"key":"e_1_2_6_24_2","unstructured":"\u00a0"},{"key":"e_1_2_6_25_2","doi-asserted-by":"publisher","DOI":"10.1021\/ja0202208"},{"key":"e_1_2_6_26_2","doi-asserted-by":"publisher","DOI":"10.1021\/jp971645x"},{"key":"e_1_2_6_27_2","doi-asserted-by":"publisher","DOI":"10.1006\/jcat.2002.3618"},{"key":"e_1_2_6_28_2","unstructured":"\u00a0"},{"key":"e_1_2_6_29_2","doi-asserted-by":"publisher","DOI":"10.1039\/b207645d"},{"key":"e_1_2_6_30_2","doi-asserted-by":"publisher","DOI":"10.1021\/cm021380l"},{"key":"e_1_2_6_31_2","unstructured":"\u00a0"},{"key":"e_1_2_6_32_2","doi-asserted-by":"publisher","DOI":"10.1002\/1099-0682(200010)2000:10<2263::AID-EJIC2263>3.0.CO;2-U"},{"key":"e_1_2_6_33_2","doi-asserted-by":"publisher","DOI":"10.1039\/b109678h"},{"key":"e_1_2_6_34_2","doi-asserted-by":"publisher","DOI":"10.1021\/jp971366"},{"key":"e_1_2_6_35_2","unstructured":"\u00a0"},{"key":"e_1_2_6_36_2","doi-asserted-by":"publisher","DOI":"10.1038\/359710a0"},{"key":"e_1_2_6_37_2","doi-asserted-by":"publisher","DOI":"10.1021\/ja00053a020"},{"key":"e_1_2_6_38_2","doi-asserted-by":"publisher","DOI":"10.1021\/jp970077i"},{"key":"e_1_2_6_39_2","doi-asserted-by":"publisher","DOI":"10.1021\/cm980440d"},{"key":"e_1_2_6_40_2","unstructured":"\u00a0"},{"key":"e_1_2_6_41_2","doi-asserted-by":"publisher","DOI":"10.1016\/0927-6513(96)00016-8"},{"key":"e_1_2_6_42_2","doi-asserted-by":"publisher","DOI":"10.1016\/S1387-1811(98)00222-4"},{"key":"e_1_2_6_43_2","unstructured":"S. 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