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|標題:||Synthesis, structures, magnetism and electrochemical properties of triruthenium-acetylide complexes||作者:||Kuo, C.K.
|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.||摘要:||
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.
|Appears in Collections:||化學系所|
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