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Complex <jats:bold>1<\/jats:bold> acts as a precatalyst and is more effective with <jats:italic>tert<\/jats:italic>\u2010butylhydroperoxide (TBHP) as the oxidant than with aq. hydrogen peroxide: the <jats:italic>cis<\/jats:italic>\u2010cyclooctene (Cy) reaction with TBHP gave 98\u2009% epoxide yield at 70 \u00b0C\/24 h. Catalyst characterization showed that <jats:bold>1<\/jats:bold> is transformed in situ to the oxidodiperoxido complex [MoO(O<jats:sub>2<\/jats:sub>)<jats:sub>2<\/jats:sub>(pbim)] (<jats:bold>2<\/jats:bold>), with H<jats:sub>2<\/jats:sub>O<jats:sub>2<\/jats:sub> and a hybrid molybdenum(VI) oxide solid formulated as [MoO<jats:sub>3<\/jats:sub>(pbim)] (<jats:bold>3<\/jats:bold>) with TBHP. The hybrid material <jats:bold>3<\/jats:bold> was prepared on a larger scale and explored for the epoxidation of the biorenewable olefins methyl oleate, methyl linoleate, and (<jats:italic>R<\/jats:italic>)\u2010(+)\u2010limonene. With TBHP as the oxidant, <jats:bold>3<\/jats:bold> acts as a source of soluble active species of the type <jats:bold>2<\/jats:bold>. A practical method for recycling oxidodiperoxidomolybdenum(VI) catalysts for the Cy\/TBHP reaction is demonstrated by using an ionic liquid as the solvent for the molecular catalyst <jats:bold>2<\/jats:bold>.<\/jats:p>","DOI":"10.1002\/ejic.201700286","type":"journal-article","created":{"date-parts":[[2017,4,6]],"date-time":"2017-04-06T13:55:22Z","timestamp":1491486922000},"page":"2617-2627","update-policy":"https:\/\/doi.org\/10.1002\/crossmark_policy","source":"Crossref","is-referenced-by-count":25,"title":["Chemistry and Catalytic Performance of Pyridyl\u2010Benzimidazole Oxidomolybdenum(VI) Compounds in (Bio)Olefin Epoxidation"],"prefix":"10.1002","volume":"2017","author":[{"ORCID":"https:\/\/orcid.org\/0000-0002-1932-4975","authenticated-orcid":false,"given":"Patr\u00edcia","family":"Neves","sequence":"first","affiliation":[{"name":"Department of Chemistry CICECO \u2013 Aveiro Institute of Materials University of Aveiro  Campus Universit\u00e1rio de Santiago 3810\u2010193 Aveiro Portugal"}]},{"ORCID":"https:\/\/orcid.org\/0000-0003-3898-401X","authenticated-orcid":false,"given":"Lucie S.","family":"Nogueira","sequence":"additional","affiliation":[{"name":"Department of Chemistry CICECO \u2013 Aveiro Institute of Materials University of Aveiro  Campus Universit\u00e1rio de Santiago 3810\u2010193 Aveiro Portugal"}]},{"ORCID":"https:\/\/orcid.org\/0000-0001-9598-1275","authenticated-orcid":false,"given":"Ana C.","family":"Gomes","sequence":"additional","affiliation":[{"name":"Department of Chemistry CICECO \u2013 Aveiro Institute of Materials University of Aveiro  Campus Universit\u00e1rio de Santiago 3810\u2010193 Aveiro Portugal"}]},{"given":"T\u00e2nia S. 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