DFT analysis of the linkage isomerism in penta(ammine)ruthenium(II/III) complexes of benzotriazole : Natural bond orbital method approach and a comprehensive energy decomposition analysis
© 2019 Wiley Periodicals, Inc.
| Veröffentlicht in: | Journal of computational chemistry. - 1984. - 40(2019), 16 vom: 15. Juni, Seite 1593-1598 |
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| Weitere Verfasser: | , , |
| Format: | Online-Aufsatz |
| Sprache: | English |
| Veröffentlicht: |
2019
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| Zugriff auf das übergeordnete Werk: | Journal of computational chemistry |
| Schlagworte: | Journal Article DFT EDA NBO benzotriazole linkage isomerization ruthenium penta(ammine) |
| Zusammenfassung: | © 2019 Wiley Periodicals, Inc. Penta(ammine)ruthenium benzotriazole complexes [RuII/III (NH3 )5 bta]+/2+ and [RuII/III (NH3 )5 btaH]2+/3+ (bta and btaH are the deprotonated and neutral form of the triazole ligand, respectively) can exhibit two linkage isomers κN1 and κN2. This system was investigated by density functional theory natural bond orbitals analysis and Su-Li energy decomposition analysis. Steric, electrostatic, exchange, repulsion, polarization, and dispersion energy components of the total metal-ligand interaction were quantitatively evaluated, and revealed that the overall metal-triazole ligand is comprised of donor-acceptor interactions like σ-donation and π-back-donation, which favors a specific isomer depending on the oxidation state of the ruthenium and the charge of the ligand. Further, activation energies (ΔG‡ ) for linkage isomerization reactions were calculated. Results were correlated with experimental chemical-electrochemical data and two plausible mechanisms are discussed. © 2019 Wiley Periodicals, Inc |
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| Beschreibung: | Date Revised 20.11.2019 published: Print-Electronic Citation Status PubMed-not-MEDLINE |
| ISSN: | 1096-987X |
| DOI: | 10.1002/jcc.25810 |