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Article

Substrate–Solvent Crosstalk—Effects on Reaction Kinetics and Product Selectivity in Olefin Oxidation Catalysis

1
Centro de Química Estrutural, Faculdade de Ciências da Universidade de Lisboa, 1749-016 Lisboa, Portugal
2
ISIS Neutron & Muon Source, Rutherford Appleton Laboratory, Chilton, Didcot, Oxfordshire OX11 0QX, UK
3
CICECO—Aveiro Institute of Materials, Department of Chemistry, University of Aveiro, 3810-193 Aveiro, Portugal
4
Champalimaud Foundation, Champalimaud Centre for the Unknown, 1400-038 Lisboa, Portugal
*
Authors to whom correspondence should be addressed.
Academic Editor: José Antonio Odriozola
Chemistry 2021, 3(3), 753-764; https://doi.org/10.3390/chemistry3030054
Received: 18 June 2021 / Revised: 14 July 2021 / Accepted: 16 July 2021 / Published: 19 July 2021
(This article belongs to the Section Catalysis)
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–solvent 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. View Full-Text
Keywords: oxidation catalysis; neutron diffraction; molybdenum; mesoporous materials; hydrogen bonds oxidation catalysis; neutron diffraction; molybdenum; mesoporous materials; hydrogen bonds
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MDPI and ACS Style

Sales, R.N.; Callear, S.K.; Vaz, P.D.; Nunes, C.D. Substrate–Solvent Crosstalk—Effects on Reaction Kinetics and Product Selectivity in Olefin Oxidation Catalysis. Chemistry 2021, 3, 753-764. https://doi.org/10.3390/chemistry3030054

AMA Style

Sales RN, Callear SK, Vaz PD, Nunes CD. Substrate–Solvent Crosstalk—Effects on Reaction Kinetics and Product Selectivity in Olefin Oxidation Catalysis. Chemistry. 2021; 3(3):753-764. https://doi.org/10.3390/chemistry3030054

Chicago/Turabian Style

Sales, Rita N., Samantha K. Callear, Pedro D. Vaz, and Carla D. Nunes 2021. "Substrate–Solvent Crosstalk—Effects on Reaction Kinetics and Product Selectivity in Olefin Oxidation Catalysis" Chemistry 3, no. 3: 753-764. https://doi.org/10.3390/chemistry3030054

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