Further insights in DFT calculations of redox potential for iron complexes: The ferrocenium/ferrocene system

Flores‐Leonar, Martha M.; Moreno‐Esparza, Rafael; Ugalde‐Saldívar, Víctor M.; Amador‐Bedolla, Carlos

doi:10.1016/j.comptc.2016.11.023

Cited by 38 publications

(32 citation statements)

References 31 publications

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“…In order to confirm the cathodic peak associated with the reduction of Fe III to Fe II DFT calculations of the redox potential were performed with TPSS, B3LYP and ωB97X−D functionals, which were selected based on our previous calculations in the Fc + /Fc + system . The calculated redox potentials ( E calc ) for the [Fe III (bztpen)OR] 2+ with respect to the Fc + /Fc value are given in Table and compared to the experimental E cp values.…”

Section: Resultssupporting

confidence: 70%

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Correlating Properties in Iron(III) Complexes: A DFT Description of Structure, Redox Potential and Spin Crossover Phenomena

et al. 2017

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Calculations of structure, redox potential and spin transition energies were performed using DFT approximations for a series of [Fe(bztpen)OR] 2 + / + type Fe III /Fe II systems (R=Me, Et, nPr, nBu), which have a temperature dependent spin crossover behavior. These compounds exhibit changes in redox and magnetic properties, related to structural variations quite important for their possible applications among which signal generator materials stand out. Functionals B3LYP, wB97XÀD and TPSS along with PCM solvation model were evaluated for redox potential, whereas for spin crossover the TPSSh functional was also included. The multireference character of these compounds was tested as well. Calculations were compared to experimental measurements, and wB97XÀD proved able to accurately describe the geometries observed in solid state for the low spin (LS) and high spin (HS) states; moreover, it had the best correlation between calculated and experimental redox potential values. However, in the description of the spin transition energies the TPSS functional is needed to correctly describe the LS state as the observed ground state in the complexes at low temperature, which allows to calculate proper spin transition curves as a function of temperature. From these results, we obtained suitable approximations for an accurate description of redox potential and magnetic properties for the Fe III coordination compounds, which can be extended to model similar systems.

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Section: Resultssupporting

confidence: 70%

“…Within the DFT approximations employed to calculate the redox potential, B3LYP has been one of the most widely used functionals ,. However in a previous work other functionals such as ωB97X−D, were seen to provide more accurate results in the calculation of potential for the Fc + /Fc system …”

Section: Determination Of Redox and Magnetic Propertiessupporting

confidence: 58%

Correlating Properties in Iron(III) Complexes: A DFT Description of Structure, Redox Potential and Spin Crossover Phenomena

et al. 2017

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“…Nevertheless, it was shown using the DFT-based A λ diagnostic [58] that DFT treatment of ferrocenium is adequate. [59] In the present study, we performed some other known multireference diagnostics for all the compounds involved in the reactions under study (Table 4). The first one is the T 1 diagnostic.…”

Section: Multireference Treatment Of the Electronic Structuresmentioning

confidence: 99%

DFT, DLPNO‐CCSD(T), and NEVPT2 benchmark study of the reaction between ferrocenium and trimethylphosphine

Chamkin

Serkova

2020

J Comput Chem

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The reaction between ferrocenium and trimethylphosphine was studied using density functional theory (DFT), domain‐based local pair natural orbital coupled cluster theory with single‐, double‐, and perturbative triple excitations (DLPNO‐CCSD(T)), and N‐electron valence state perturbation theory (NEVPT2). The accuracy of the DFT functionals decreases compared to the DLPNO‐CCSD(T) level in the following order: M06‐L > TPSS > M06, BLYP > PBE, PBE0, B3LYP > > PWPB95 > > DSD‐BLYP. The roles of thermochemical, continuum solvation (SMD), and counterpoise corrections were evaluated. Grimme's D3 empirical dispersion correction is essential for all functionals studied except M06 and M06‐L. The reliability of the frequency calculations performed directly within the SMD was confirmed. The systems showed no significant multireference character according to T1 and T2 diagnostics and the fractional occupation number (FOD) weighted electron density analysis. The multireference NEVPT2 calculations gave qualitatively valid conclusions about the reaction mechanism. However, a multireference approach is generally not recommended because it requires arbitrary chosen active spaces.

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“…The computational procedures employed for predicting reduction potentials can be classified in two types [ 30 , 31 , 32 , 33 , 34 , 35 , 36 , 37 , 38 , 39 ]: (i) “direct”, when the reduction potential of the half-reaction for a molecular entity M is calculated directly between their solvated oxidized (M (svt) ) and reduced (M − (svt) ) forms and (ii) “indirect”, when the calculation is based on a thermodynamic cycle ( Scheme 1 ) [ 40 ]. The direct procedure is computationally simpler but although formally correct [ 41 ], it generally leads to unsatisfactory results.…”

Section: Theoretical Fundamentalsmentioning

confidence: 99%

One-Electron Reduction Potentials: Calibration of Theoretical Protocols for Morita–Baylis–Hillman Nitroaromatic Compounds in Aprotic Media

et al. 2018

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Nitroaromatic compounds—adducts of Morita–Baylis–Hillman (MBHA) reaction—have been applied in the treatment of malaria, leishmaniasis, and Chagas disease. The biological activity of these compounds is directly related to chemical reactivity in the environment, chemical structure of the compound, and reduction of the nitro group. Because of the last aspect, electrochemical methods are used to simulate the pharmacological activity of nitroaromatic compounds. In particular, previous studies have shown a correlation between the one-electron reduction potentials in aprotic medium (estimated by cyclic voltammetry) and antileishmanial activities (measured by the IC50) for a series of twelve MBHA. In the present work, two different computational protocols were calibrated to simulate the reduction potentials for this series of molecules with the aim of supporting the molecular modeling of new pharmacological compounds from the prediction of their reduction potentials. The results showed that it was possible to predict the experimental reduction potential for the calibration set with mean absolute errors of less than 25 mV (about 0.6 kcal·mol−1).

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Further insights in DFT calculations of redox potential for iron complexes: The ferrocenium/ferrocene system

Cited by 38 publications

References 31 publications

Correlating Properties in Iron(III) Complexes: A DFT Description of Structure, Redox Potential and Spin Crossover Phenomena

Correlating Properties in Iron(III) Complexes: A DFT Description of Structure, Redox Potential and Spin Crossover Phenomena

DFT, DLPNO‐CCSD(T), and NEVPT2 benchmark study of the reaction between ferrocenium and trimethylphosphine

One-Electron Reduction Potentials: Calibration of Theoretical Protocols for Morita–Baylis–Hillman Nitroaromatic Compounds in Aprotic Media

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