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Molecular Electrochemistry of Coordination Compounds—A Correlation Between Quantum Chemical Calculations and Experiment

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Transition Metals in Coordination Environments

Part of the book series: Challenges and Advances in Computational Chemistry and Physics ((COCH,volume 29))

Abstract

This contribution shows how molecular electrochemistry may benefit from the application of DFT methods combined with implicit solvent models. The progress in quantum chemical calculations, including efficient solvation models, has brought about the development of effective computational protocols that allow accurate (to 0.05 V) reproduction of experimental redox potentials of mono- and dinuclear complexes, including electrocatalytically relevant systems and mixed-valence compounds. These calculations may also help to understand how electronic and structural factors, modulated by the changes in both first and second coordination spheres, and the local environment (dielectric medium and specific interactions), govern the ability of transition metal complexes to undergo electron transfer (ET) processes. Understanding the principles that lie behind it is of great importance in redox chemistry and catalysis, and biological systems. After a brief introduction to modelling approaches and discussion of challenges for calibration of computational protocols based on comparison with experimental data, a number of noteworthy case studies are given. Specifically, the determination of ferrocenium/ferrocene absolute potentials in solvents commonly used in electrochemistry is discussed, the redox behaviour of Cu and Fe systems affected by H-bonding, followed by the presentation of intriguing properties of mono- and bimetallic Mo/W scorpionates . Particularly, electrochemical communication between metal centres and a baffling (auto)catalytic dehalogenation triggered by ET through a C−H⋯Oalkoxide hydrogen bond, the mechanism of which was unravelled owing to the application of dispersion-corrected DFT calculations, are highlighted.

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Notes

  1. 1.

    Differences between \( E^\circ_{(\text{abs})} \)(SHE) values result from different values of the hydration free energy of H+ and the \( {\text{H}}^{ + }_{{({\text{gas}})}} \) free energy of formation. The value of 4.44 V based on experimental data at 298.15 K refers to the outer potential of the phase (Volta potential), whereas the computed values of 4.28 or 4.32 V correspond to the inner potential of the phase (Galvani potential), which is exactly what the QC results refer to. The IUPAC-recommended experimental value, (4.44 ± 0.02) V, is not very appropriate; it must differ by the value of surface potential of water from the computed data. The surface potential is not directly measurable and must be calculated. Its values range between 0.16 and 0.14 V, resulting in the Eabs(SHE) equal to 4.28 or 4.32 V. A future work may bring a new value, but not differing more than by 40 mV from the published so far.

  2. 2.

    If the liquid and gas-phase solute structures differ appreciably, using partition functions computed in solution is a correct approach, see [83].

  3. 3.

    E1/2 denotes a mean of voltammetric anodic and cathodic peak potentials. E1/2 = Ef (Ef is formal potential) if the diffusion coefficients of the oxidised (Ox) and reduced (Red) forms are equal. Ef potential refers to the situation, when the concentration ratio of [Ox] to [Red] at the electrode surface is equal to one, which obviously is not true in the case of more complex systems, like, e.g. proton-coupled reactions. Then, knowing the electrode reaction, and the concentration of that other participating species, like protons, the relation between the Ef and E° (based on concentrations) can easily be found.

  4. 4.

    Calibrated against the best available experimental data or highly accurate QM methods, such as G3(MP2)-RAD or explicitly correlated coupled cluster theory CCSD(T)-F12 calculations, which could now be applied even for midsized metal complexes, if only single reference quantum methods are applicable.

  5. 5.

    The computed potential given in [35] (−1.80 V) was obtained from calculations done in a slightly differently contracted basis set (LANL2DZ) for Mo.

  6. 6.

    Note, however, that for these species, ΔE1/2 might be larger in a less polar solvent.

  7. 7.

    Similar geometry of the {(ON)MoOMo(NO)} moiety has also been found in structurally characterised complexes with non-Tp ligands, e.g. [{MoII(NO)(‘S4’)}2(μ-O)] (‘S4’ = 2,3,8,9-dibenzo-1,4,7,10-tetrathiadecane(2−) or [Cp*Mo(NO)R]2(μ-O) (Cp* = η5-C5Me5, R = CH2SiMe3 or Me). References are given in [62].

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Acknowledgements

We thank Prof. Ewa Brocławik (Polish Academy of Sciences), Dr. Mariusz Radoń (Jagiellonian University) and Klemens Noga (Academic Computer Center CYFRONET) for a long-standing collaboration and very valuable, fruitful discussions. Support for this work from the PL-Grid Infrastructure is gratefully acknowledged.

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  1. Faculty of Chemical Engineering and Technology, Molecular Electrochemistry Group, Cracow University of Technology, ul. Warszawska 24 31-155, Kraków, Poland

    Piotr P. Romańczyk & Stefan S. Kurek

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  1. Piotr P. Romańczyk
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  2. Stefan S. Kurek
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Correspondence to Piotr P. Romańczyk .

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  1. Jerzy Haber Institute of Catalysis and Surface Chemistry, Polish Academy of Sciences, Kraków, Poland

    Ewa Broclawik

  2. Jerzy Haber Institute of Catalysis and Surface Chemistry, Polish Academy of Sciences, Kraków, Poland

    Tomasz Borowski

  3. Faculty of Chemistry, Jagiellonian University, Kraków, Poland

    Mariusz Radoń

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Romańczyk, P.P., Kurek, S.S. (2019). Molecular Electrochemistry of Coordination Compounds—A Correlation Between Quantum Chemical Calculations and Experiment. In: Broclawik, E., Borowski, T., Radoń, M. (eds) Transition Metals in Coordination Environments. Challenges and Advances in Computational Chemistry and Physics, vol 29. Springer, Cham. https://doi.org/10.1007/978-3-030-11714-6_13

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