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標題: Ru2M(dpa)(4)Cl-2 (M =Cu, Ni): Synthesis, characterization, and theoretical analysis of asymmetric heterometal string complexes of the dipyridylamide family
作者: Huang, G.C.
Benard, M.
Rohmer, M.M.
Li, L.A.
Chiu, M.J.
Yeh, C.Y.
Lee, G.H.
Peng, S.M.
關鍵字: molecular wires;mixed-metal complexes;metal-metal interactions;magnetic properties;electrochemistry;density functional calculations;linear tricobalt compounds;density-functional theory;magnetic-properties;chain complexes;metal complexes;solid-state;bonds;dpa;ligands;wires
Project: European Journal of Inorganic Chemistry
期刊/報告no:: European Journal of Inorganic Chemistry, Issue 11, Page(s) 1767-1777.
Four heterotrinuclear strings of metal atoms stabilized by dipyridylamide (dpa(-)) ligands were synthesized and characterized. The metal frameworks of Ru2Cu(dpa)(4)CI2 (1), its monooxidized counterpart [Ru2Cu(dpa)(4)Cl-2]PF6 (2), and their nickel homologues, Ru2Ni(dpa)(4)Cl-2 (3) and [Ru2Ni(dpa)(4)Cl-2]-PF6 (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 (Ru2M](6+) framework of 1 and 3 was shown from spectroelectrochemical analysis and DFT calculations to exist in the form of a mixed-valent [Ru2](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. (C) Wiley-VCH Verlag GmbH & Co. KGaA, 69451 Weinheim, Germany, 2008)
ISSN: 1434-1948
DOI: 10.1002/ejic.200701159
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