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Rocha, Reginaldo C.; Araki, Koji; Toma, Henrique E.

doi:10.1023/a:1006985329436

Cited by 21 publications

(11 citation statements)

References 12 publications

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“…The reactivity of the benzotriazole and benzotriazolate mononuclear derivatives was already discussed elsewhere [17][18][19] . The benzimidazole/benzimidazolate species, on the other hand, are being reported for the first time.…”

Section: Resultsmentioning

confidence: 99%

“…Since increasing the charge of the cation usually stabilizes the anionic conjugate base, it follows that the coordinated ligand becomes more acidic when the charge of the cation is increased. Therefore, the acid dissociation constant (K a ) of the complex increases with the oxidation state of the metal 19,33 . Consequently, a metal-localized redox process shows a pH-dependent couple if deprotonation (protonation) of the ligand occurs upon oxidation (reduction) of the complex in the pH range studied.…”

Section: Discussionmentioning

confidence: 99%

“…This process has been assigned [17][18][19] to 17,19 , only the redox potentials associated with the reversible wave (M III/II -N3-btaH couple) will be taken for all purposes involving proton-dependence related features.…”

Section: Complexes [Ru Iiiii (Edta)(lh)] -2-and [Ru Iiiii (Edta)(lmentioning

confidence: 99%

“…Although the reactivity and the properties of transition metal complexes with imidazole and triazole derivatives have been studied over the last decades, a few cases involving the interaction of the benzimidazole (bimH) and benzotriazole (btaH) ligands (Scheme 1) with iron(II,III) and ruthenium(II,III) complexes are known [16][17][18][19][20][21][22] . Actually, to the best of our knowledge, we have investigated the coordination chemistry of benzotriazole with pentacyano-ferrate(II)/ (III) 17,21 , pentaammineruthenium(II)/(III) 18,21,22 and ethylenediaminetetraacetatoruthenium (II)/(III) 19,20,22 for the first time.…”

Section: Introductionmentioning

confidence: 99%

“…Actually, to the best of our knowledge, we have investigated the coordination chemistry of benzotriazole with pentacyano-ferrate(II)/ (III) 17,21 , pentaammineruthenium(II)/(III) 18,21,22 and ethylenediaminetetraacetatoruthenium (II)/(III) 19,20,22 for the first time. In this present work, a larger series involving these metal units was studied, by including a structural analogue of the benzotriazole ligand (namely, benzimidazole).…”

Section: Introductionmentioning

confidence: 99%

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Ruthenium and iron complexes with benzotriazole and benzimidazole derivatives as simple models for proton-coupled electron transfer systems

Rocha

Rein

Toma

2001

J. Braz. Chem. Soc.

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(CN) 5 3-,2-and LH = benzotriazole or benzimidazole) were prepared and characterized in aqueous solutions by means of electrochemical and spectroelectrochemical methods. Special emphasis was given to the pH-dependent redox processes, exhibited by all the investigated complexes. From their related Pourbaix diagrams, which displayed a typically Nernstian behavior, the pK a and formal reduction potential values were extracted. In addition, these E 1/2 versus pH curves were also used to illustrate the partitioning relationship concerning the redox and acid-base species, and their interconversion equilibria. The active area in which the dependence of the M III /M II couple on the pH takes place, as delimited by pK a III and pK a II , was taken into account in order to evaluate the usefulness of such simple complexes as models for proton-coupled electron transfer (PCET). The results were interpreted in terms of the acceptor/ donor electronic character of the ligands and σ,π-metal-ligand interactions in both redox states of the metal ion.

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Section: Resultsmentioning

confidence: 99%

Section: Discussionmentioning

confidence: 99%

Section: Complexes [Ru Iiiii (Edta)(lh)] -2-and [Ru Iiiii (Edta)(lmentioning

confidence: 99%

Section: Introductionmentioning

confidence: 99%

Section: Introductionmentioning

confidence: 99%

See 3 more Smart Citations

Ruthenium and iron complexes with benzotriazole and benzimidazole derivatives as simple models for proton-coupled electron transfer systems

Rocha

Rein

Toma

2001

J. Braz. Chem. Soc.

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Molecular Materials and Devices: Developing New Functional Systems Based on the Coordination Chemistry Approach

Toma

2004

ChemInform

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Neste limiar da era nanotecnológica, o planejamento molecular dos materiais e os estudos de moléculas isoladas estão abrindo imensas possibilidades no emprego de sistemas moleculares em dispositivos eletrônicos e fotônicos, bem como em aplicações tecnológicas baseadas em propriedades de chaveamento ou reconhecimento molecular. Com esse escopo, os químicos inorgânicos em particular, podem aplicar com vantagens as estratégias proporcionadas pela química de coordenação, para construir nanomateriais funcionais que permitam a exploração das propriedades dos centros metálicos e das características dos ligantes presentes. A química de coordenação também oferece recursos eficientes na auto-montagem de nanoestruturas, baseadas na especificidade da interação metal-ligante e nas características estereoquímicas dos complexos. Diversos materiais moleculares gerados a partir de compostos inorgânicos e metal-orgânicos são focalizados neste artigo, com ênfase em novas porfirinas e porfirazinas supramoleculares, clusters e complexos metálicos. Tais sistemas também são enfocados sob o ponto de vista de suas aplicações em catálise, sensores e dispositivos moleculares.At the onset of the nanotechnology age, molecular designing of materials and single molecule studies are opening wide possibilities of using molecular systems in electronic and photonic devices, as well as in technological applications based on molecular switching or molecular recognition. In this sense, inorganic chemists are privileged by the possibility of using the basic strategies of coordination chemistry to build up functional supramolecular materials, conveying the remarkable chemical properties of the metal centers and the characteristics of the ancillary ligands. Coordination chemistry also provides effective self-assembly strategies based on specific metal-ligand affinity and stereochemistry. Several molecular based materials, derived from inorganic and metal-organic compounds are focused on this article, with emphasis on new supramolecular porphyrins and porphyrazines, metal-clusters and metal-polyimine complexes. Such systems are also discussed in terms of their applications in catalysis, sensors and molecular devices.

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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

et al. 2019

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Penta(ammine)ruthenium benzotriazole complexes [RuII/III(NH3)5bta]+/2+ and [RuII/III(NH3)5btaH]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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Cited by 21 publications

References 12 publications

Ruthenium and iron complexes with benzotriazole and benzimidazole derivatives as simple models for proton-coupled electron transfer systems

Ruthenium and iron complexes with benzotriazole and benzimidazole derivatives as simple models for proton-coupled electron transfer systems

Molecular Materials and Devices: Developing New Functional Systems Based on the Coordination Chemistry Approach

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

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