Please use this identifier to cite or link to this item: http://hdl.handle.net/11455/67918
標題: Oxidation of linear trinuclear ruthenium complexes Ru-3(dpa)(4)Cl-2 and Ru-3(dpa)(4)(CN)(2) : Synthesis, structures, electrochemical and magnetic properties
作者: Kuo, C.K.
Liu, I.P.C.
Yeh, C.Y.
Chou, C.H.
Tsao, T.B.
Lee, G.H.
Peng, S.M.
關鍵字: density functional calculations
metal-metal interactions
multiple
bonds
N ligands
ruthenium
metal string complexes
di(2-pyridyl)amide dpa ligands
crystal-structure
tripyridyldiamido dianion
electronic-properties
tricobalt compounds
bonds
compound
tetrapyridyltriamine
ni-3(dpa)(4)cl-2
期刊/報告no:: Chemistry-a European Journal, Volume 13, Issue 5, Page(s) 1442-1451.
摘要: The neutral, monocationic, and dicationic linear trinuclear ruthenium compounds [Ru-3(dpa)(4)(CN)(2)], [Ru-3(dpa)(4)(CN)(2)][BF4], [Ru-3(dpa)(4)Cl-2]- [BF4], and [Ru-3(dpa)(4)Cl-2][BF4](2) (dpa = the anion of dipyridylamine) have been synthesized and characterized by various spectroscopic techniques. Cyclic voltammetric and spectroelectrochemical studies on the neutral and oxidized compounds are reported. These compounds undergo three successive metal-centered one-electron-transfer processes. X-ray structural studies reveal a symmetrical Ru-3 unit for these compounds. While the metal-metal bond lengths change only slightly, the metal-axial ligand lengths exhibit a significant decrease upon oxidation of the neutral complex. The electronic configuration of the Ru-3 unit changes as the axial chloride ligands are replaced by the stronger "pi-acid" cyanide axial ligands. Magnetic measurements and H-1 NMR spectra indicate that [Ru-3(dpa)(4)Cl-2] and [Ru-3(dpa)(4)Cl-2][BF4](2) are in a spin state of S = 0 and [Ru-3-(dpa)(4)Cl-2][BF4], [Ru-3(dpa)(4)(CN)(2)], and [Ru-3(dpa)(4)(CN)(2)][BF4] are in spin states of S=1/2, 1, and 3/2, respectively. These results are consistent with molecular orbital (MO) calculations.
URI: http://hdl.handle.net/11455/67918
ISSN: 0947-6539
文章連結: http://dx.doi.org/10.1002/chem.200601219
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