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標題: Synthesis, structures, magnetism and electrochemical properties of triruthenium-acetylide complexes
作者: Kuo, C.K.
Chang, J.C.
Yeh, C.Y.
Lee, G.H.
Wang, C.C.
Peng, S.M.
關鍵字: metal string complexes;sigma-alkynyl complexes;molecular wires;diruthenium compounds;electron-transfer;crystal-structure;ligands;chains;bearing;family
Project: Dalton Transactions
期刊/報告no:: Dalton Transactions, Issue 22, Page(s) 3696-3701.
A series of triruthenium complexes with arylacetylide axial ligands Ru-3(dpa)(4)(C2X)(2)(BF4)(y) (dpa = dipyridylamido; X = Fc, y = 0 ( 1); X = Ph, y = 0 ( 2); X = PhOCH3, y = 1 ( 3); X = PhC5H11, y = 1 ( 4); X = PhCN, y = 0 ( 5); X = PhNO2, y = 0 ( 6)) have been synthesized. The crystal structures show that the Ru-Ru bond lengths (2.3304(9)-2.3572(5) angstrom) of these compounds are longer than those of Ru-3(dpa)(4)Cl-2 (Ru-Ru = 2.2537(1) angstrom). This is ascribed to the formation of the stronger pi-backbonding from metal to axial ligand which weakens the Ru-Ru interactions and the bond order is reduced in the triruthenium unit. Cyclic voltammetry and differential pulse voltammetry show that compound 1 exhibits electronic coupling between the two ferrocenyl units with Delta E-1/2 close to 100 mV. Compounds 2-6 display three triruthenium-based reversible one-electron redox couples, two oxidations and one reduction, and the electrode potentials shift upon varying the substituents. A linear relationship is observed when the Hammett constants are plotted against the redox potentials.
ISSN: 1477-9226
DOI: 10.1039/b506267e
Appears in Collections:化學系所

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