Ru2M(dpa)4Cl2 (M = Cu, Ni): Synthesis, characterization, and theoretical analysis of asymmetric heterometal string complexes of the dipyridylamide family
Resource
European Journal of Inorganic Chemistry 2008 (11): 1767-1777
Journal
European Journal of Inorganic Chemistry
Journal Issue
11
Pages
1767-1777
Date Issued
2008
Author(s)
Huang, Gin-Chen
Bénard, Marc
Rohmer, Marie-Madeleine
Li, Long-An
Yunu, Mei-Jchi
Yeh, Chen-Yu
Lee, Gene-Hsiang
Abstract
Abstract Four heterotrinuclear strings of metal atoms stabilized by dipyridylamide (dpa – ) ligands were synthesized and characterized. The metal frameworks of Ru 2 Cu(dpa) 4 Cl 2 ( 1 ), its monooxidized counterpart [Ru 2 Cu(dpa) 4 Cl 2 ]PF 6 ( 2 ), and their nickel homologues, Ru 2 Ni(dpa) 4 Cl 2 ( 3 ) and [Ru 2 Ni(dpa) 4 Cl 2 ]PF 6 ( 4 ), were shown by X‐ray diffraction to be nonsymmetric, in spite of a severe disorder affecting the metal positions. The metal string is composed of a Ru dimer with a short Ru–Ru bond that is completed with the heterometal at a longer distance from the central ruthenium atom. This nonsymmetric structure was confirmed from NMR spectroscopy. The [Ru 2 M] 6+ framework of 1 and 3 was shown from spectroelectrochemical analysis and DFT calculations to exist in the form of a mixed‐valent [Ru 2 ] 5+ moiety coupled to a formally M + heterometal. The temperature‐dependant magnetic susceptibility of these compounds is reported and interpreted by means of a model previously applied to [Ru 2 ] 5+ complexes. The redox chemistry of 1 and 3 was investigated by cyclic voltammetry, and the electronic structure of the mono‐ and dioxidized species was assigned from the observed changes in the UV/Vis spectra and from DFT calculations.(© Wiley‐VCH Verlag GmbH & Co. KGaA, 69451 Weinheim, Germany, 2008)
Type
journal article
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Ru2M (dpa) 4Cl2 (M =Cu, Ni) Synthesis, characterization, and theoretical analysis of asymmetric heterometal string complexes of the dipyridylamide family.pdf
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