Computational Study on Homolytic Bond Energies of the Ag-X (X = C, O, and H) Complexes and Hammett-Type Analysis of Reactivity.

Thirty-seven calculation methods were benchmarked against the available experimental bond lengths and energies data regarding the Ag-X bonds. The theoretical protocol PBE0/VDZ//ωB97x-D/mVTZ was found to be capable of accurately predicting the homolytic bond dissociation energies (BDEs) of Ag-X complexes with a precision of 1.9 kcal/mol. With the available method in hand, a wide range of different Ag-X BDEs were estimated. BDE(Ag-CH 2 X), BDE(Ag-PhX), BDE(Ag-OPhX), and BDE(Ag-OCOPhX) (X = NH 2 , OMe, Me, H, Cl, and NO 2 ) were found to be in the ranges of 27-47, 51-54, 19-39, and 64-70 kcal/mol, respectively. Subsequently, Hammett-type analysis was carried out with reactivity parameters. Good positive linear relationships were found for BDE of Ag-O bands and decarboxylation barriers of Ag-OCOPhX with the Hammett constant σ. It suggested that electron-donating substituents could promote either the homolytic cleavage of the Ag-OPhX bond to undergo a radical process or Ag-OCOPhX decarboxylation. Moreover, ligand effects on Ag-H bonds were investigated using BDE(Ag-H) and related NPA charges on Ag. In the case of P-ligands, carbene ligands, and other small molecule ligands (i.e., CO, CO 2 , and H 2 O), a good negative linear relationship was found. In contrast, N-ligands could have a reverse effect. Understanding the intrinsic relationships of BDE(Ag-X) with related reactivity parameters might help gain insights into the structure-reactivity relationships in Ag-X-assisted C-H activation/decarboxylation.