84333 20230914083234.0 doi 10.1080/00268976.2018.1542168 sideral 109099 ART-2018-109099 eng Munárriz, J. Universidad de Zaragoza (orcid)0000-0001-6089-6126 A bonding evolution theory study on the catalytic Noyori hydrogenation reaction 2018 Access copy available to the general public Unrestricted The electronic rearrangements involved in Noyori hydrogenation reactions with double bonds (ethene and formaldehyde) are analysed using the bonding evolution theory. The study and analysis of the changes on the electron localisation function topology along a given reaction path reveals fluxes of electron density, allowing to unambiguously identify the main chemical events happening along the chemical reactions. This analysis shows that the first hydrogen transfer (with hydride character) occurs before the transition state (TS), while the second hydrogen transfer (with proton character) takes places after having reached the TS. The lower energy barrier found for formaldehyde over ethene is explained by two reasons. First, the hydride transfer is favoured for the C = O bond over C = C due to the electrophilic character of the carbon atom. Second, a negatively charged CH3–X (X = CH2, O) hidden intermediate is formed in the proximities of the TS region. The oxygen atom is able to stabilise this negatively charged species more effectively than the CH2 group due to its higher electronegativity and the presence of V(O) lone pairs. The obtained analysis explains and rationalises catalyst chemoselectivity (C = O vs. C = C). Finally, a curly arrow representation diagram accounting for the electronic rearrangements is proposed on the basis of BET results. info:eu-repo/grantAgreement/ES/MEC/FPU14-06003 info:eu-repo/grantAgreement/ES/MINECO/CTQ2015-67366-P info:eu-repo/semantics/openAccess All rights reserved http://www.europeana.eu/rights/rr-f/ 1.571 2018 PHYSICS, ATOMIC, MOLECULAR & CHEMICAL 28 / 36 = 0.778 2018 Q4 T3 CHEMISTRY, PHYSICAL 114 / 147 = 0.776 2018 Q4 T3 0.635 2018 Biophysics 2018 Q2 Physical and Theoretical Chemistry 2018 Q2 Molecular Biology 2018 Q2 Condensed Matter Physics 2018 Q2 info:eu-repo/semantics/article info:eu-repo/semantics/acceptedVersion Laplaza, R. Polo, V. Universidad de Zaragoza (orcid)0000-0001-5823-7965 2012 755 Universidad de Zaragoza Dpto. Química Física Área Química Física 117, 9-12 (2018), 1315 - 1324 Mol. phys. MOLECULAR PHYSICS 0026-8976 498864 http://zaguan.unizar.es/record/84333/files/texto_completo.pdf Postprint 41867 http://zaguan.unizar.es/record/84333/files/texto_completo.jpg?subformat=icon icon Postprint oai:zaguan.unizar.es:84333 articulos driver 2023-09-13-10:45:04 ARTICLE