Dataset Information

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

ABSTRACT: 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-CH₂X), BDE(Ag-PhX), BDE(Ag-OPhX), and BDE(Ag-OCOPhX) (X = NH₂, OMe, Me, H, Cl, and NO₂) 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, CO₂, and H₂O), 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.

SUBMITTER: Wu L

PROVIDER: S-EPMC8697619 | biostudies-literature | 2021 Dec

REPOSITORIES: biostudies-literature

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Publications

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

Wu Lei L Tang Shi-Ya SY Zhou Shaodong S

ACS omega 20211207 50

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<sub>2</sub>X), BDE(Ag-PhX), BDE(Ag-OPhX), and BDE(Ag-OCOPhX) (X ...[more]

PMID: 34963973

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Project description:Applicability of Hammett parameters (σ m and σ p ) was tested in extended π-systems in gas phase. Three different model graphene systems, viz. 5,5-graphene (GR), 3-B-5,5-graphene (3BGR), and 3-N-5,5-graphene (3NGR), were designed as extended π-systems, and interactions of various nitrobenzene derivatives (mainly m- and p-substituted together with some multiple substitutions) on such platforms were monitored using density functional theory (M06/cc-pVDZ, M06/cc-pVTZ, M06/sp-aug-cc-pVTZ) and Møller-Plesset second-order perturbation (MP2/cc-pV-DZ) theory. Offset face to face (OSFF) stackings were found to be the favored orientations, and reasonable correlations were found between binding energies (ΔE B) and the ∑|σ m | values of the substituted nitrobenzenes. It was proposed previously that |σ m | contains information about the substituents' polarizability and controls electrostatic and dispersion interactions. The combination of ∑|σ m | and molar refractivity (as ∑M r) or change in polarizability (Δα: with respect to benzene) of nitrobenzene derivatives generated statistically significant correlation with respect to ΔE B, thereby supporting the hypothesis related to the validity of |σ m | correlations. The |σ p | parameters also maintain similar correlations for the various p-substituted nitrobenzene derivatives together with several multiply-substituted nitrobenzene derivatives. The correlation properties in such cases are similar to the |σ m | cases, and the energy partition analysis for both the situations reveled importance of electrostatic and dispersion contributions in such interactions. The applicability of Hammett parameters was observed previously on the restricted parallel face to face orientation of benzene···substituted benzene systems, and the present results show that such an idea could be used to predict ΔE B values in OSFF orientations, if the scaffolds are designed in such a way that substituted benzene systems cannot escape their π-clouds.

Dataset Information

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

Publications

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

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