{"status":"ok","message-type":"work","message-version":"1.0.0","message":{"indexed":{"date-parts":[[2026,10,4]],"date-time":"2026-10-04T02:57:24Z","timestamp":1791082644291,"version":"4.1.0"},"reference-count":51,"publisher":"Wiley","issue":"31","license":[{"start":{"date-parts":[[2010,5,21]],"date-time":"2010-05-21T00:00:00Z","timestamp":1274400000000},"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":[[2010,8,16]]},"abstract":"<jats:title>Abstract<\/jats:title><jats:p>Compounds [Cp*<jats:sub>2<\/jats:sub>M<jats:sub>2<\/jats:sub>O<jats:sub>5<\/jats:sub>] (M=Mo, <jats:bold>1<\/jats:bold>; W, <jats:bold>2<\/jats:bold>) are efficient pre\u2010catalysts for cyclooctene (COE) epoxidation by aqueous H<jats:sub>2<\/jats:sub>O<jats:sub>2<\/jats:sub> in acetonitrile\/toluene. The reaction is quantitative, selective and takes place approximately 50 times faster for the W system (<jats:italic>k<\/jats:italic><jats:sub>obs<\/jats:sub>=4.32(9)\u00d710<jats:sup>\u22124<\/jats:sup>\u2005s<jats:sup>\u22121<\/jats:sup> at 55\u2009\u00b0C and 3\u00d710<jats:sup>\u22123<\/jats:sup>\u2009<jats:sc>M<\/jats:sc> concentration for the dinuclear complex, vs. 1.06(7)\u00d710<jats:sup>\u22125<\/jats:sup>\u2005s<jats:sup>\u22121<\/jats:sup> for the Mo system). The rate law is first order in catalyst and COE substrate (<jats:italic>k<\/jats:italic>=0.138(7)\u2005<jats:sc>M<\/jats:sc><jats:sup>\u22121<\/jats:sup>\u2009s<jats:sup>\u22121<\/jats:sup> for the W system at 55\u2009\u00b0C), whereas increasing the concentration of H<jats:sub>2<\/jats:sub>O<jats:sub>2<\/jats:sub> slows down the reaction because of an inhibiting effect of the greater amount of water. The activation parameters for the more active W systems (\u0394<jats:italic>H<\/jats:italic><jats:sup>\u2260<\/jats:sup>=10.2(6)\u2005kcal\u2009mol<jats:sup>\u22121<\/jats:sup>; \u0394<jats:italic>S<\/jats:italic><jats:sup>\u2260<\/jats:sup>=\u221232(2)\u2005cal\u2009mol<jats:sup>\u22121<\/jats:sup>\u2009K<jats:sup>\u22121<\/jats:sup>) were obtained from an Eyring study in the 25\u201355\u2009\u00b0C temperature range. The H<jats:sub>2<\/jats:sub>O<jats:sub>2<\/jats:sub>\u22c5urea adduct was less efficient as an oxidant than the aqueous H<jats:sub>2<\/jats:sub>O<jats:sub>2<\/jats:sub> solution. Replacement of toluene with diethyl ether did not significantly affect the catalyst efficiency, whereas replacement with THF slowed down the process. The epoxidation of ethylene as a model olefin, catalysed by the [Cp*MO<jats:sub>2<\/jats:sub>Cl] systems (M=W, Mo) in the presence of H<jats:sub>2<\/jats:sub>O<jats:sub>2<\/jats:sub> as oxidant and acetonitrile as solvent, has been investigated by DFT calculations with the use of the conductor\u2010like polarisable continuum model (CPCM). For both metal systems, the rate\u2010limiting step is the transfer of the hydroperoxido O<jats:sup>\u03b1<\/jats:sup> atom to the olefin, in accordance with the first\u2010order dependence on the substrate and the zero\u2010order dependence on H<jats:sub>2<\/jats:sub>O<jats:sub>2<\/jats:sub> found experimentally in the catalytic data. The activation barrier corresponding to the rate\u2010limiting step is 4\u2005kcal lower for the W complex than for the corresponding Mo analogue (32.3 vs. 28.3\u2005kcal\u2009mol<jats:sup>\u22121<\/jats:sup>). This result reproduces well the higher catalytic activity of the W species. The different catalytic behaviour between the two systems is rationalised by a natural bond orbital (NBO) study and natural population analyses (NPA). Compared to Mo, the W<jats:sup>VI<\/jats:sup> centre withdraws more electron density from the \u03c3 bonding [O\uf8ffO] orbital and favours, as a consequence, the nucleophilic attack of the external olefin on the \u03c3*[O\uf8ffO] orbital.<\/jats:p>","DOI":"10.1002\/chem.201000298","type":"journal-article","created":{"date-parts":[[2010,5,25]],"date-time":"2010-05-25T03:25:40Z","timestamp":1274757940000},"page":"9572-9584","source":"Crossref","is-referenced-by-count":77,"title":["Olefin Epoxidation by H<sub>2<\/sub>O<sub>2<\/sub>\/MeCN Catalysed by Cyclopentadienyloxidotungsten(VI) and Molybdenum(VI) Complexes: Experiments and Computations"],"prefix":"10.1002","volume":"16","author":[{"given":"Chiara","family":"Dinoi","sequence":"first","affiliation":[],"role":[{"vocabulary":"crossref","role":"author"}]},{"given":"Marco","family":"Ciclosi","sequence":"additional","affiliation":[],"role":[{"vocabulary":"crossref","role":"author"}]},{"given":"Eric","family":"Manoury","sequence":"additional","affiliation":[],"role":[{"vocabulary":"crossref","role":"author"}]},{"given":"Laurent","family":"Maron","sequence":"additional","affiliation":[],"role":[{"vocabulary":"crossref","role":"author"}]},{"given":"Lionel","family":"Perrin","sequence":"additional","affiliation":[],"role":[{"vocabulary":"crossref","role":"author"}]},{"given":"Rinaldo","family":"Poli","sequence":"additional","affiliation":[],"role":[{"vocabulary":"crossref","role":"author"}]}],"member":"311","published-online":{"date-parts":[[2010,8,12]]},"reference":[{"key":"e_1_2_6_1_2","doi-asserted-by":"publisher","DOI":"10.1002\/chem.200304810"},{"key":"e_1_2_6_2_2","doi-asserted-by":"publisher","DOI":"10.1039\/9781847551641-00167"},{"key":"e_1_2_6_3_2","doi-asserted-by":"publisher","DOI":"10.1016\/j.jorganchem.2007.05.021"},{"key":"e_1_2_6_4_2","doi-asserted-by":"publisher","DOI":"10.1039\/B202106B"},{"key":"e_1_2_6_5_2","doi-asserted-by":"publisher","DOI":"10.1021\/ic062409g"},{"key":"e_1_2_6_6_2","doi-asserted-by":"publisher","DOI":"10.1021\/om049107b"},{"key":"e_1_2_6_7_2","doi-asserted-by":"publisher","DOI":"10.1021\/om0300023"},{"key":"e_1_2_6_8_2","doi-asserted-by":"publisher","DOI":"10.1016\/j.molcata.2004.07.023"},{"key":"e_1_2_6_9_2","doi-asserted-by":"publisher","DOI":"10.1016\/j.jorganchem.2005.10.044"},{"key":"e_1_2_6_10_2","doi-asserted-by":"publisher","DOI":"10.1016\/j.jorganchem.2006.05.007"},{"key":"e_1_2_6_11_2","doi-asserted-by":"publisher","DOI":"10.1016\/j.jorganchem.2006.03.037"},{"key":"e_1_2_6_12_2","doi-asserted-by":"publisher","DOI":"10.1021\/om8009206"},{"key":"e_1_2_6_13_2","doi-asserted-by":"publisher","DOI":"10.1021\/cr020471z"},{"key":"e_1_2_6_14_2","doi-asserted-by":"publisher","DOI":"10.1021\/cr00082a005"},{"key":"e_1_2_6_15_2","doi-asserted-by":"publisher","DOI":"10.1021\/ic00323a021"},{"key":"e_1_2_6_16_2","doi-asserted-by":"publisher","DOI":"10.1021\/ic00347a013"},{"key":"e_1_2_6_17_2","doi-asserted-by":"publisher","DOI":"10.1039\/dt9940003511"},{"key":"e_1_2_6_18_2","doi-asserted-by":"publisher","DOI":"10.1021\/ic970544a"},{"key":"e_1_2_6_19_2","doi-asserted-by":"publisher","DOI":"10.1021\/ja973917f"},{"key":"e_1_2_6_20_2","doi-asserted-by":"publisher","DOI":"10.1021\/ic971426q"},{"key":"e_1_2_6_21_2","doi-asserted-by":"publisher","DOI":"10.1021\/om800035f"},{"key":"e_1_2_6_22_2","doi-asserted-by":"publisher","DOI":"10.1002\/chem.200902873"},{"key":"e_1_2_6_23_2","doi-asserted-by":"publisher","DOI":"10.1021\/om00050a058"},{"key":"e_1_2_6_24_2","doi-asserted-by":"publisher","DOI":"10.1021\/om980732o"},{"key":"e_1_2_6_25_2","first-page":"302","volume":"7","author":"Iogansen A. 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