{"status":"ok","message-type":"work","message-version":"1.0.0","message":{"indexed":{"date-parts":[[2026,3,9]],"date-time":"2026-03-09T08:16:44Z","timestamp":1773044204758,"version":"3.50.1"},"reference-count":48,"publisher":"MDPI AG","issue":"3","license":[{"start":{"date-parts":[[2021,7,19]],"date-time":"2021-07-19T00:00:00Z","timestamp":1626652800000},"content-version":"vor","delay-in-days":0,"URL":"https:\/\/creativecommons.org\/licenses\/by\/4.0\/"}],"funder":[{"DOI":"10.13039\/501100001871","name":"Funda\u00e7\u00e3o para a Ci\u00eancia e a Tecnologia","doi-asserted-by":"publisher","award":["UIDB\/00100\/2020"],"award-info":[{"award-number":["UIDB\/00100\/2020"]}],"id":[{"id":"10.13039\/501100001871","id-type":"DOI","asserted-by":"publisher"}]},{"DOI":"10.13039\/501100001871","name":"Funda\u00e7\u00e3o para a Ci\u00eancia e a Tecnologia","doi-asserted-by":"publisher","award":["UIDP\/00100\/2020"],"award-info":[{"award-number":["UIDP\/00100\/2020"]}],"id":[{"id":"10.13039\/501100001871","id-type":"DOI","asserted-by":"publisher"}]}],"content-domain":{"domain":[],"crossmark-restriction":false},"short-container-title":["Chemistry"],"abstract":"<jats:p>In this work, we explored how solvents can affect olefin oxidation reactions catalyzed by MCM-bpy-Mo catalysts and whether their control can be made with those players. The results of this study demonstrated that polar and apolar aprotic solvents modulated the reactions in different ways. Experimental data showed that acetonitrile (aprotic polar) could largely hinder the reaction rate, whereas toluene (aprotic apolar) did not. In both cases, product selectivity at isoconversion was not affected. Further insights were obtained by means of neutron diffraction experiments, which confirmed the kinetic data and allowed for the proposal of a model based on substrate\u2013solvent crosstalk by means of hydrogen bonding. In addition, the model was also validated in the ring-opening reaction (overoxidation) of styrene oxide to benzaldehyde, which progressed when toluene was the solvent (reaching 31% styrene oxide conversion) but was strongly hindered when acetonitrile was used instead (reaching only 7% conversion) due to the establishment of H-bonds in the latter. Although this model was confirmed and validated for olefin oxidation reactions, it can be envisaged that it may also be applied to other catalytic reaction systems where reaction control is critical, thereby widening its use.<\/jats:p>","DOI":"10.3390\/chemistry3030054","type":"journal-article","created":{"date-parts":[[2021,7,19]],"date-time":"2021-07-19T04:55:40Z","timestamp":1626670540000},"page":"753-764","update-policy":"https:\/\/doi.org\/10.3390\/mdpi_crossmark_policy","source":"Crossref","is-referenced-by-count":7,"title":["Substrate\u2013Solvent Crosstalk\u2014Effects on Reaction Kinetics and Product Selectivity in Olefin Oxidation Catalysis"],"prefix":"10.3390","volume":"3","author":[{"given":"Rita N.","family":"Sales","sequence":"first","affiliation":[{"name":"Centro de Qu\u00edmica Estrutural, Faculdade de Ci\u00eancias da Universidade de Lisboa, 1749-016 Lisboa, Portugal"}]},{"given":"Samantha K.","family":"Callear","sequence":"additional","affiliation":[{"name":"ISIS Neutron & Muon Source, Rutherford Appleton Laboratory, Chilton, Didcot, Oxfordshire OX11 0QX, UK"}]},{"ORCID":"https:\/\/orcid.org\/0000-0001-9720-9801","authenticated-orcid":false,"given":"Pedro D.","family":"Vaz","sequence":"additional","affiliation":[{"name":"CICECO\u2014Aveiro Institute of Materials, Department of Chemistry, University of Aveiro, 3810-193 Aveiro, Portugal"},{"name":"Champalimaud Foundation, Champalimaud Centre for the Unknown, 1400-038 Lisboa, Portugal"}]},{"ORCID":"https:\/\/orcid.org\/0000-0001-8750-7813","authenticated-orcid":false,"given":"Carla D.","family":"Nunes","sequence":"additional","affiliation":[{"name":"Centro de Qu\u00edmica Estrutural, Faculdade de Ci\u00eancias da Universidade de Lisboa, 1749-016 Lisboa, Portugal"}]}],"member":"1968","published-online":{"date-parts":[[2021,7,19]]},"reference":[{"key":"ref_1","doi-asserted-by":"crossref","first-page":"120161","DOI":"10.1016\/j.ica.2020.120161","article-title":"Optimizing noble metals exploitation in water oxidation catalysis by their incorporation in layered double hydroxides","volume":"516","author":"Zaccaria","year":"2021","journal-title":"Inorg. 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