Synthesis, crystal structures and electrochemical properties of CoIII complexes with hexadentate ligand containing thioether-amidopyridyl donor set

被引:3
作者
Amirnasr, Mehdi [1 ]
Rasouli, Mahdieh [1 ]
Mereiter, Kurt [2 ]
机构
[1] Isfahan Univ Technol, Dept Chem, Esfahan 8415683111, Iran
[2] Vienna Univ Technol, Fac Chem, A-1060 Vienna, Austria
基金
美国国家科学基金会;
关键词
Amide-thioether; Cobalt(III) complexes; C-S bond cleavage; X-ray crystal structure; Cyclic voltammetry; S BOND-CLEAVAGE; COBALT(III) COMPLEXES; CARBOXAMIDE LIGANDS; NICKEL-COMPLEXES; AMIDE LIGAND; NITRIC-OXIDE; COORDINATION; PYRIDINE; CHEMISTRY; COPPER;
D O I
10.1007/s13738-012-0156-6
中图分类号
O6 [化学];
学科分类号
0703 ;
摘要
Two new cobalt(III) complexes of the hexadentate ligand [1,4-bis[o-(pyridine-2-carboxamidophenyl)]-1,4-dithiobutane] (H(2)bpctb) with N4S2 donor set atoms have been synthesized. A reaction of Co(CH3COO)(2)center dot 4H(2)O with (H(2)bpctb) leads to the formation of [Co-III(bpctb)]PF6 (1) having a CoN2(pyridine)N'(2)(amide)S-2(thioether) coordination by symmetric bpctb(2-) ligand. A similar reaction under slightly different conditions, however, gives [Co-III(L (a) )(L (b) )] (2), resulting from a C-S bond cleavage reaction triggered by an acetate ion as a base, having CoN2(pyridine)N'(2)(amide)S(thioether)S'(thiolate) coordination. These two Co(III) complexes have been characterized by elemental analyses and spectroscopic methods, and the crystal and molecular structures of [Co-III(bpctb)]PF6 (1) in the form of the solvate (1 center dot MeOH center dot H2O) and of [Co-III(L (a) )(L (b) )] (2) have been determined by X-ray crystallography. The Co atoms of both complexes exhibit distorted octahedral geometry. The electrochemical investigation of [Co(bpctb)]PF6 center dot MeOH center dot H2O (1 center dot MeOH center dot H2O) and [Co-III(L (a) )(L (b) )] (2) by cyclic voltammetry reveals a reversible Co-III-Co-II redox process at E (1/2) = -0.32 V (Delta E (p) = 80 mV); for 1, and E (1/2) = -0. 87 V (Delta E (p) = 70 mV) for 2.
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页码:275 / 282
页数:8
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