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The complexes were applied as catalysts in the homogeneous phase for the epoxidation of cyclooctene, with <jats:italic>tert<\/jats:italic>\u2010butyl hydroperoxide (TBHP) as the oxygen source. The desired epoxide was the only product and turnover frequencies of up to about 9000 h<jats:sup>\u20131<\/jats:sup> could be reached. The catalytic activities increased in the order [MoO<jats:sub>2<\/jats:sub>Br<jats:sub>2<\/jats:sub>(dmbp)] &lt; [MoO<jats:sub>2<\/jats:sub>Br<jats:sub>2<\/jats:sub>(hmbp)] &lt; [MoO<jats:sub>2<\/jats:sub>Cl<jats:sub>2<\/jats:sub>(dmbp)] &lt; [MoO<jats:sub>2<\/jats:sub>Cl<jats:sub>2<\/jats:sub>(hmbp)]. A kinetic model was built up for a homogeneous batch reactor based on a simplified mechanism involving three steps: (i) reversible coordination of TBHP to the starting Mo<jats:sup>VI<\/jats:sup> complex to give a Mo<jats:sup>VI<\/jats:sup> alkylperoxide; (ii) irreversible oxidation of cyclooctene to cyclooctene oxide by the species formed in step 1, with formation of the starting complex and <jats:italic>tert<\/jats:italic>\u2010butyl alcohol; (iii) reversible coordination of <jats:italic>tert<\/jats:italic>\u2010butyl alcohol to the starting complex. This model is consistent with the observed kinetics. The first step in this reaction mechanism was characterized in more detail by studying the kinetics of the reaction of the starting complexes with TBHP in the absence of any reductant by UV\/Vis spectroscopy. Rate constants, equilibrium constants, and activation parameters were determined. All \u0394<jats:italic>S<\/jats:italic><jats:sup>\u2021<\/jats:sup> values were negative and therefore support an associative mechanism in which a seven\u2010coordinate intermediate is formed. The results also suggest that the first step is not always the rate\u2010limiting step of cyclooctene epoxidation with these complexes. (\u00a9 Wiley\u2010VCH Verlag GmbH &amp; Co. KGaA, 69451 Weinheim, Germany, 2005)<\/jats:p>","DOI":"10.1002\/ejic.200400852","type":"journal-article","created":{"date-parts":[[2005,4,28]],"date-time":"2005-04-28T11:21:19Z","timestamp":1114687279000},"page":"1716-1723","update-policy":"https:\/\/doi.org\/10.1002\/crossmark_policy","source":"Crossref","is-referenced-by-count":74,"title":["Kinetics of Cyclooctene Epoxidation with <i>tert<\/i>\u2010Butyl Hydroperoxide in the Presence of [MoO<sub>2<\/sub>X<sub>2<\/sub>L]\u2010Type Catalysts (L = Bidentate Lewis Base)"],"prefix":"10.1002","volume":"2005","author":[{"given":"Ahmad","family":"Al\u2010Ajlouni","sequence":"first","affiliation":[]},{"given":"Anabela A.","family":"Valente","sequence":"additional","affiliation":[]},{"given":"Carla D.","family":"Nunes","sequence":"additional","affiliation":[]},{"given":"Martyn","family":"Pillinger","sequence":"additional","affiliation":[]},{"given":"Ana M.","family":"Santos","sequence":"additional","affiliation":[]},{"given":"Jin","family":"Zhao","sequence":"additional","affiliation":[]},{"given":"Carlos C.","family":"Rom\u00e3o","sequence":"additional","affiliation":[]},{"given":"Isabel S.","family":"Gon\u00e7alves","sequence":"additional","affiliation":[]},{"given":"Fritz E.","family":"K\u00fchn","sequence":"additional","affiliation":[]}],"member":"311","published-online":{"date-parts":[[2005,4,28]]},"reference":[{"key":"e_1_2_6_1_2","unstructured":"\u00a0"},{"key":"e_1_2_6_2_2","doi-asserted-by":"publisher","DOI":"10.1039\/dt9910002169"},{"key":"e_1_2_6_3_2","doi-asserted-by":"publisher","DOI":"10.1039\/C39900000531"},{"key":"e_1_2_6_4_2","doi-asserted-by":"publisher","DOI":"10.1021\/ja00506a044"},{"key":"e_1_2_6_5_2","doi-asserted-by":"publisher","DOI":"10.1021\/ja00290a030"},{"key":"e_1_2_6_6_2","doi-asserted-by":"publisher","DOI":"10.1021\/ja00284a073"},{"key":"e_1_2_6_7_2","doi-asserted-by":"publisher","DOI":"10.1021\/om00008a043"},{"key":"e_1_2_6_8_2","doi-asserted-by":"publisher","DOI":"10.1039\/DT9950001221"},{"key":"e_1_2_6_9_2","doi-asserted-by":"publisher","DOI":"10.1039\/dt9950001489"},{"key":"e_1_2_6_10_2","doi-asserted-by":"publisher","DOI":"10.1039\/dt9950003329"},{"volume-title":"Lehrbuch der Anorganischen Chemie","year":"1995","author":"Hollemann A. 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