Ligand and solvent effects on CO2 insertion into group 10 metal alkyl bonds

Anthony P Deziel; Matthew R Espinosa; Ljiljana Pavlovic; David J Charboneau; Nilay Hazari; Kathrin H Hopmann; Brandon Q Mercado

doi:10.1039/d1sc06346d

Ligand and solvent effects on CO₂ insertion into group 10 metal alkyl bonds

Chem Sci. 2022 Feb 9;13(8):2391-2404. doi: 10.1039/d1sc06346d. eCollection 2022 Feb 23.

Authors

Anthony P Deziel¹, Matthew R Espinosa¹, Ljiljana Pavlovic², David J Charboneau¹, Nilay Hazari¹, Kathrin H Hopmann², Brandon Q Mercado¹

Affiliations

¹ Department of Chemistry, Yale University P. O. Box 208107 New Haven Connecticut 06520 USA nilay.hazari@yale.edu.
² Department of Chemistry, UiT The Arctic University of Norway N-9307 Tromsø Norway kathrin.hopmann@uit.no.

Abstract

The 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 (^RPBP)M(CH₃) (^RPBP = B(NCH₂PR₂)₂C₆H₄ ^-; R = Cy or ^t Bu; M = Ni or Pd) to generate κ¹-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 ( ^{^t Bu}PBP)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 ( ^{^t Bu}PBP)M(CH₃) (M = Ni or Pd) proceeds via an S_E2 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.