A Series of Copper Complexes of a Dinucleating Bis(tetradentate) Nitrogen Ligand: Synthesis, Structural, Spectroscopic, Electrochemical, and Magnetic Characterization

Limpke T, Butenuth C, Stammler A, Bögge H, Glaser T (2017)
EUROPEAN JOURNAL OF INORGANIC CHEMISTRY 2017(29): 3570-3579.

Zeitschriftenaufsatz | Veröffentlicht | Englisch
 
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Abstract / Bemerkung
The dinucleating ligand "susan" [4,7-dimethyl-1,1,10,10-tetra(2-pyridylmethyl)-1,4,7,10-tetraazadecane] has been used for the synthesis of a series of dinuclear Cu-II complexes with varying exogenous ligands: [(susan){Cu(MeCN)} 2](ClO4)(4), [(susan){CuCl}(2)]Cl-2, [(susan){CuBr}(2)]Br-2, [(susan){Cu(mu-OH) Cu}](ClO4)(3), and [(susan){Cu(mu-OH) Cu}](PF6)(3). In the solid state, the Cu-II ions are trigonal-bipyramidally coordinated in [(susan){Cu(mu-OH) Cu}](3+), whereas they are in a square-pyramidal environment in the other complexes although mononuclear CuII complexes are trigonal-bipyramidal. In solution, all complexes are trigonal-bipyramidal; only [(susan){Cu(MeCN)}(2)](4+) is distorted even in solution. The UV/Vis spectra exhibit unique charge-transfer (CT) transitions, which make them easy to iden-tify in solution. Complex [(susan){Cu(MeCN)}(2)](4+) exhibits two reversible reductive processes, demonstrating access to a (CuCuI)-Cu-I complex, whereas the other complexes exhibit only one reductive process. Complexes [(susan){Cu(mu-OH) Cu}](ClO4)(3) and [(susan){Cu(mu-OH)Cu}](PF6)(3) exhibit strong antiferromagnetic interactions with coupling constants of J = -247 and -234 cm(-1), respectively. These data are compared to mononuclear analogs and discussed with respect to the steric flexibility of the ligand backbone and influence of intramolecular interactions on the properties of the dinuclear complexes. Complex [(susan){Cu(mu-OH)Cu}](3+) catalyzes the aerobic oxidation of 3,5-di-tert-butylcatechol in the presence and absence of a base.
Stichworte
Dinucleating ligands; N ligands; Copper; Ligand effects; Electrochemistry
Erscheinungsjahr
2017
Zeitschriftentitel
EUROPEAN JOURNAL OF INORGANIC CHEMISTRY
Band
2017
Ausgabe
29
Seite(n)
3570-3579
ISSN
1434-1948
eISSN
1099-0682
Page URI
https://pub.uni-bielefeld.de/record/2913979

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Limpke T, Butenuth C, Stammler A, Bögge H, Glaser T. A Series of Copper Complexes of a Dinucleating Bis(tetradentate) Nitrogen Ligand: Synthesis, Structural, Spectroscopic, Electrochemical, and Magnetic Characterization. EUROPEAN JOURNAL OF INORGANIC CHEMISTRY. 2017;2017(29):3570-3579.
Limpke, T., Butenuth, C., Stammler, A., Bögge, H., & Glaser, T. (2017). A Series of Copper Complexes of a Dinucleating Bis(tetradentate) Nitrogen Ligand: Synthesis, Structural, Spectroscopic, Electrochemical, and Magnetic Characterization. EUROPEAN JOURNAL OF INORGANIC CHEMISTRY, 2017(29), 3570-3579. doi:10.1002/ejic.201700732
Limpke, T., Butenuth, C., Stammler, A., Bögge, H., and Glaser, T. (2017). A Series of Copper Complexes of a Dinucleating Bis(tetradentate) Nitrogen Ligand: Synthesis, Structural, Spectroscopic, Electrochemical, and Magnetic Characterization. EUROPEAN JOURNAL OF INORGANIC CHEMISTRY 2017, 3570-3579.
Limpke, T., et al., 2017. A Series of Copper Complexes of a Dinucleating Bis(tetradentate) Nitrogen Ligand: Synthesis, Structural, Spectroscopic, Electrochemical, and Magnetic Characterization. EUROPEAN JOURNAL OF INORGANIC CHEMISTRY, 2017(29), p 3570-3579.
T. Limpke, et al., “A Series of Copper Complexes of a Dinucleating Bis(tetradentate) Nitrogen Ligand: Synthesis, Structural, Spectroscopic, Electrochemical, and Magnetic Characterization”, EUROPEAN JOURNAL OF INORGANIC CHEMISTRY, vol. 2017, 2017, pp. 3570-3579.
Limpke, T., Butenuth, C., Stammler, A., Bögge, H., Glaser, T.: A Series of Copper Complexes of a Dinucleating Bis(tetradentate) Nitrogen Ligand: Synthesis, Structural, Spectroscopic, Electrochemical, and Magnetic Characterization. EUROPEAN JOURNAL OF INORGANIC CHEMISTRY. 2017, 3570-3579 (2017).
Limpke, Thomas, Butenuth, Christoph, Stammler, Anja, Bögge, Hartmut, and Glaser, Thorsten. “A Series of Copper Complexes of a Dinucleating Bis(tetradentate) Nitrogen Ligand: Synthesis, Structural, Spectroscopic, Electrochemical, and Magnetic Characterization”. EUROPEAN JOURNAL OF INORGANIC CHEMISTRY 2017.29 (2017): 3570-3579.