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dc.contributor.authorDeziel, Anthony P.
dc.contributor.authorEspinosa, Matthew
dc.contributor.authorPavlovic, Ljiljana
dc.contributor.authorCharboneau, David J.
dc.contributor.authorHazari, Nilay
dc.contributor.authorHopmann, Kathrin Helen
dc.contributor.authorMercado, Brandon Q.
dc.date.accessioned2022-03-30T11:48:23Z
dc.date.available2022-03-30T11:48:23Z
dc.date.issued2022-02-09
dc.description.abstractThe insertion of carbon dioxide into metal element σ-bonds is an important elementary step in many catalytic reactions for carbon dioxide valorization. Here, the insertion of carbon dioxide into a family of group 10 alkyl complexes of the type (<sup>R</sup>PBP)M(CH<sub>3</sub>) (<sup>R</sup>PBP = B(NCH<sub>2</sub>PR<sub>2</sub>)<sub>2</sub>C<sub>6</sub>H<sub>4</sub><sup>−</sup>; R = Cy or <sup>t</sup>Bu; M = Ni or Pd) to generate κ<sup>1</sup>-acetate complexes of the form (<sup>R</sup>PBP)M{OC(O)CH<sub>3</sub>} is investigated. This involved the preparation and characterization of a number of new complexes supported by the unusual <sup>R</sup>PBP ligand, which features a central boryl donor that exerts a strong trans-influence, and the identification of a new decomposition pathway that results in C–B bond formation. In contrast to other group 10 methyl complexes supported by pincer ligands, carbon dioxide insertion into (<sup>R</sup>PBP)M(CH<sub>3</sub>) is facile and occurs at room temperature because of the high trans-influence of the boryl donor. Given the mild conditions for carbon dioxide insertion, we perform a rare kinetic study on carbon dioxide insertion into a late-transition metal alkyl species using (<sup>tBu</sup>PBP)Pd(CH<sub>3</sub>). These studies demonstrate that the Dimroth–Reichardt parameter for a solvent correlates with the rate of carbon dioxide insertion and that Lewis acids do not promote insertion. DFT calculations indicate that insertion into (<sup>tBu</sup>PBP)M(CH<sub>3</sub>) (M = Ni or Pd) proceeds via an S<sub>E</sub>2 mechanism and we compare the reaction pathway for carbon dioxide insertion into group 10 methyl complexes with insertion into group 10 hydrides. Overall, this work provides fundamental insight that will be valuable for the development of improved and new catalysts for carbon dioxide utilization.en_US
dc.identifier.citationDeziel, Espinosa M, Pavlovic Lj, Charboneau DJ, Hazari N, Hopmann KH, Mercado BQ. Ligand and solvent effects on CO2 insertion into group 10 metal alkyl bonds. Chemical Science. 2022;13:2391-2404en_US
dc.identifier.cristinIDFRIDAID 2006891
dc.identifier.doihttps://doi.org/10.1039/D1SC06346D
dc.identifier.issn2041-6520
dc.identifier.issn2041-6539
dc.identifier.urihttps://hdl.handle.net/10037/24653
dc.language.isoengen_US
dc.publisherRoyal Society of Chemistryen_US
dc.relation.journalChemical Science
dc.relation.urifile:///C:/Users/admin/Downloads/d1sc06346d.pdf
dc.rights.accessRightsopenAccessen_US
dc.rights.holderCopyright 2022 The Author(s)en_US
dc.titleLigand and solvent effects on CO2 insertion into group 10 metal alkyl bondsen_US
dc.type.versionpublishedVersionen_US
dc.typeJournal articleen_US
dc.typeTidsskriftartikkelen_US
dc.typePeer revieweden_US


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