Molecular Electrochemistry
of Coordination
Compounds—A Correlation Between
Quantum Chemical Calculations
and Experiment
Piotr P. Roma ´
nczyk and Stefan S. Kurek
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· · ·O alkoxide hydrogen bond, the mechanism of which
was unravelled owing to the application of dispersion-corrected DFT calculations,
are highlighted.
P. P. Roma´ nczyk (B) · S. S. Kurek
Faculty of Chemical Engineering and Technology, Molecular Electrochemistry Group,
Cracow University of Technology, ul. Warszawska 24 31-155, Kraków, Poland
e-mail: piotrom@chemia.pk.edu.pl
S. S. Kurek
e-mail: skurek@chemia.pk.edu.pl
© Springer Nature Switzerland AG 2019
E. Broclawik et al. (eds.), Transition Metals in Coordination Environments,
Challenges and Advances in Computational Chemistry and Physics 29,
https://doi.org/10.1007/978-3-030-11714-6_13
409
of Coordination
Compounds—A Correlation Between
Quantum Chemical Calculations
and Experiment
Piotr P. Roma ´
nczyk and Stefan S. Kurek
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· · ·O alkoxide hydrogen bond, the mechanism of which
was unravelled owing to the application of dispersion-corrected DFT calculations,
are highlighted.
P. P. Roma´ nczyk (B) · S. S. Kurek
Faculty of Chemical Engineering and Technology, Molecular Electrochemistry Group,
Cracow University of Technology, ul. Warszawska 24 31-155, Kraków, Poland
e-mail: piotrom@chemia.pk.edu.pl
S. S. Kurek
e-mail: skurek@chemia.pk.edu.pl
© Springer Nature Switzerland AG 2019
E. Broclawik et al. (eds.), Transition Metals in Coordination Environments,
Challenges and Advances in Computational Chemistry and Physics 29,
https://doi.org/10.1007/978-3-030-11714-6_13
409