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dc.contributor.authorPavlovic, Ljiljana
dc.contributor.authorVaitla, Janakiram
dc.contributor.authorBayer, Annette
dc.contributor.authorHopmann, Kathrin Helen
dc.date.accessioned2019-01-16T15:00:39Z
dc.date.available2019-01-16T15:00:39Z
dc.date.issued2018-03-12
dc.description.abstractThe mechanism of rhodium-COD-catalyzed hydrocarboxylation of styrene derivatives and α,β-unsaturated carbonyl compounds with CO<sub>2</sub> has been investigated using density functional theory (PBE-D2/IEFPCM). The calculations support a catalytic cycle as originally proposed by Mikami and co-workers including β-hydride elimination, insertion of the unsaturated substrate into a rhodium–hydride bond, and subsequent carboxylation with CO<sub>2</sub>. The CO<sub>2</sub> insertion step is found to be rate limiting. The calculations reveal two interesting aspects. First, during C–CO<sub>2</sub> bond formation, the CO<sub>2</sub> molecule interacts with neither the rhodium complex nor the organozinc additive. This appears to be in contrast to other CO<sub>2</sub> insertion reactions, where CO<sub>2</sub>–metal interactions have been predicted. Second, the substrates show an unusual coordination mode during CO<sub>2</sub> insertion, with the nucleophilic carbon positioned up to 3.6 Å away from rhodium. In order to understand the experimentally observed substrate preferences, we have analyzed a set of five alkenes: an α,β-unsaturated ester, an α,β-unsaturated amide, styrene, and two styrene derivatives. The computational results and additional experiments reported here indicate that the lack of activity with amides is caused by an overly high barrier for CO<sub>2</sub> insertion and is not due to catalyst inactivation. Our experimental studies also reveal two putative side reactions, involving oxidative cleavage or dimerization of the alkene substrate. In the presence of CO<sub>2</sub>, these alternative reaction pathways are suppressed. The overall insights may be relevant for the design of future hydrocarboxylation catalysts.en_US
dc.description.sponsorshipThe Tromsø Research Foundation Notur-The Norwegian Metacenter for Computational Science NordForsken_US
dc.descriptionAccepted manuscript version of the following article: Pavlovic, L., Vaitla, J., Bayer, A. & Hopmann, K.H. (2018). Rhodium-Catalyzed Hydrocarboxylation: Mechanistic Analysis Reveals Unusual Transition State for Carbon–Carbon Bond Formation. <i>Organometallics</i>, 37(6), 941-948. Published version available at <a href=https://doi.org/10.1021/acs.organomet.7b00899> https://doi.org/10.1021/acs.organomet.7b00899</a>.en_US
dc.identifier.citationPavlovic, L., Vaitla, J., Bayer, A. & Hopmann, K.H. (2018). Rhodium-Catalyzed Hydrocarboxylation: Mechanistic Analysis Reveals Unusual Transition State for Carbon–Carbon Bond Formation. <i>Organometallics</i>, 37(6), 941-948. https://doi.org/10.1021/acs.organomet.7b00899en_US
dc.identifier.cristinIDFRIDAID 1572392
dc.identifier.doi10.1021/acs.organomet.7b00899
dc.identifier.issn0276-7333
dc.identifier.issn1520-6041
dc.identifier.urihttps://hdl.handle.net/10037/14465
dc.language.isoengen_US
dc.publisherAmerican Chemical Societyen_US
dc.relation.ispartofPavlovic, L. (2020). Towards Enantioselective Carboxylation and Hydrogenation Reactions (Quantum Chemical Modelling of Homogeneous Reactions). (Doctoral thesis). <a href=https://hdl.handle.net/10037/18943>https://hdl.handle.net/10037/18943</a>.
dc.relation.journalOrganometallics
dc.relation.projectIDinfo:eu-repo/grantAgreement/RCN/SFF/262695/Norway/Hylleraas Centre for Quantum Molecular Sciences//en_US
dc.relation.projectIDinfo:eu-repo/grantAgreement/RCN/FRINATEK/231706/Norway/"Eeny, meeny, miny, moe": Selectivity-determining factors in asymmetric catalysis//en_US
dc.relation.urihttps://pubs.acs.org/doi/10.1021/acs.organomet.7b00899
dc.rights.accessRightsopenAccessen_US
dc.subjectVDP::Mathematics and natural science: 400::Chemistry: 440en_US
dc.subjectVDP::Matematikk og Naturvitenskap: 400::Kjemi: 440en_US
dc.titleRhodium-Catalyzed Hydrocarboxylation: Mechanistic Analysis Reveals Unusual Transition State for Carbon–Carbon Bond Formationen_US
dc.typeJournal articleen_US
dc.typeTidsskriftartikkelen_US
dc.typePeer revieweden_US


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