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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
Author(s) -
Costa Gouveia Tiago Leyser,
Campos Renan Borsoi,
Ribeiro Ronny Rocha,
Nunes Fábio Souza
Publication year - 2019
Publication title -
journal of computational chemistry
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 0.907
H-Index - 188
eISSN - 1096-987X
pISSN - 0192-8651
DOI - 10.1002/jcc.25810
Subject(s) - chemistry , linkage isomerism , ruthenium , benzotriazole , natural bond orbital , deprotonation , ligand (biochemistry) , steric effects , density functional theory , isomerization , computational chemistry , molecular orbital , photochemistry , metal , stereochemistry , molecule , ion , organic chemistry , catalysis , biochemistry , receptor
Penta(ammine)ruthenium benzotriazole complexes [Ru II/III (NH 3 ) 5 bta] +/2+ and [Ru II/III (NH 3 ) 5 btaH] 2+/3+ (bta and btaH are the deprotonated and neutral form of the triazole ligand, respectively) can exhibit two linkage isomers κ N1 and κ N2 . 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 (Δ G ‡ ) for linkage isomerization reactions were calculated. Results were correlated with experimental chemical–electrochemical data and two plausible mechanisms are discussed. © 2019 Wiley Periodicals, Inc.