Molecular and electronic structures of a series of Dinuclear Co-II Complexes varied by exogeneous ligands: Influence of pi-bonding on redox potentials

Depenbrock F, Limpke T, Stammler A, Oldengott J, Bögge H, Glaser T (2022)
European Journal of Inorganic Chemistry 2022(6): e202100992.

Zeitschriftenaufsatz | Veröffentlicht | Englisch
 
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Abstract / Bemerkung
Four dinuclear Co-II complexes have been synthesized and structurally characterized with the dinucleating ligand susan (susan - 4,7-di methyl-1,1,10,10-tetra(2-pyridyl methyl)-1,4,7,1 0tetraazadecane) varying in the exogeneous ligands: [(susan)- {Co-II(CH3CN)(2)}(2)](PF6)(4), [(susan){Co-II Cl)(2)](ClO4)(2), [(susan)- {(CoBr)-Br-II}(2)](ClO4)(2), and [(susan){Co-II(mu-OH)COII}](ClO4)(3). The Co-II ions are six-coordinate with CH,CN ligands and five-coordinate with anionic ligands. The electronic absorption spectra reflect the differences in the electronic structures, not only between the six- and five-coordinate complexes, but also between the fivecoordinate complexes. These variations are also reflected in the magnetic properties with the highest orbital angular momen tum contribution in six-coordinate [(susan){Co-II(CH3CN)(2)}(2)](PF6)(4). The lower symmetry in the five-coordinate complexes reduces the orbital angular momentum contribution. The hydroxobridged complex [(susan){Co-II(mu-OH)COII}](ClO4)(3) exhibits an additional antiferromagnetic interaction. The electrochemical characterization reveals that the pi-acceptor ligand CH3CN facilitates not only reduction from Co-II to COI but also oxidation to Co-III while the pi-donor ligands Br-, Cl-, and mu-OH impede both reduction to COI and oxidation to Co-III. [(susan){Co-II- (CH3CN)(2)}(2)](PF6)(4) and [(susan){(CoCl)-Cl-II}(2)](ClO4)(2) show electrocata- lytic proton reduction at a potential of approximate to - 1.9 V vs Fc(+)/Fc that is associated with a ligand-centered reduction.
Erscheinungsjahr
2022
Zeitschriftentitel
European Journal of Inorganic Chemistry
Band
2022
Ausgabe
6
Art.-Nr.
e202100992
ISSN
1434-1948
eISSN
1099-0682
Page URI
https://pub.uni-bielefeld.de/record/2961626

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Depenbrock F, Limpke T, Stammler A, Oldengott J, Bögge H, Glaser T. Molecular and electronic structures of a series of Dinuclear Co-II Complexes varied by exogeneous ligands: Influence of pi-bonding on redox potentials. European Journal of Inorganic Chemistry . 2022;2022(6): e202100992.
Depenbrock, F., Limpke, T., Stammler, A., Oldengott, J., Bögge, H., & Glaser, T. (2022). Molecular and electronic structures of a series of Dinuclear Co-II Complexes varied by exogeneous ligands: Influence of pi-bonding on redox potentials. European Journal of Inorganic Chemistry , 2022(6), e202100992. https://doi.org/10.1002/ejic.202100992
Depenbrock, F., Limpke, T., Stammler, A., Oldengott, J., Bögge, H., and Glaser, T. (2022). Molecular and electronic structures of a series of Dinuclear Co-II Complexes varied by exogeneous ligands: Influence of pi-bonding on redox potentials. European Journal of Inorganic Chemistry 2022:e202100992.
Depenbrock, F., et al., 2022. Molecular and electronic structures of a series of Dinuclear Co-II Complexes varied by exogeneous ligands: Influence of pi-bonding on redox potentials. European Journal of Inorganic Chemistry , 2022(6): e202100992.
F. Depenbrock, et al., “Molecular and electronic structures of a series of Dinuclear Co-II Complexes varied by exogeneous ligands: Influence of pi-bonding on redox potentials”, European Journal of Inorganic Chemistry , vol. 2022, 2022, : e202100992.
Depenbrock, F., Limpke, T., Stammler, A., Oldengott, J., Bögge, H., Glaser, T.: Molecular and electronic structures of a series of Dinuclear Co-II Complexes varied by exogeneous ligands: Influence of pi-bonding on redox potentials. European Journal of Inorganic Chemistry . 2022, : e202100992 (2022).
Depenbrock, Felix, Limpke, Thomas, Stammler, Anja, Oldengott, Jan, Bögge, Hartmut, and Glaser, Thorsten. “Molecular and electronic structures of a series of Dinuclear Co-II Complexes varied by exogeneous ligands: Influence of pi-bonding on redox potentials”. European Journal of Inorganic Chemistry 2022.6 (2022): e202100992.

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