Cristin-resultat-ID: 2006891
Sist endret: 25. mai 2022, 11:07
NVI-rapporteringsår: 2022
Vitenskapelig artikkel

Ligand and solvent effects on CO2insertion into group 10 metal alkyl bonds

  • Anthony P. Deziel
  • Matthew Espinosa
  • Ljiljana Pavlovic
  • David J. Charboneau
  • Nilay Hazari
  • Kathrin Helen Hopmann
  • mfl.


Chemical Science
ISSN 2041-6520
e-ISSN 2041-6539
NVI-nivå 2

Om resultatet

Vitenskapelig artikkel
Publiseringsår: 2022
Publisert online: 2022
Trykket: 2022
Volum: 13
Hefte: 8
Sider: 2391 - 2404
Open Access


Scopus-ID: 2-s2.0-85125569740

Beskrivelse Beskrivelse


Ligand and solvent effects on CO2insertion into group 10 metal alkyl bonds


The insertion of carbon dioxide into metal element s-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 (RPBP)M(CH3) (RPBP ¼ B(NCH2PR2)2C6H4-; R ¼ Cy or tBu; M ¼ Ni or Pd) to generate k1-acetate complexes of the form (RPBP)M{OC(O)CH3} is investigated. This involved the preparation and characterization of a number of new complexes supported by the unusual RPBP 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 (RPBP)M(CH3) 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 (tBuPBP)Pd(CH3). 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 (tBuPBP)M(CH3) (M ¼ Ni or Pd) proceeds via an SE2 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.


Anthony P. Deziel

  • Tilknyttet:

Matthew Espinosa

  • Tilknyttet:

Ljiljana Pavlovic

  • Tilknyttet:
    ved Institutt for kjemi ved UiT Norges arktiske universitet

David J. Charboneau

  • Tilknyttet:

Nilay Hazari

  • Tilknyttet:
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