Synthesis, Spectral Characterization and Electrochemical Properties of New vic-dioxime Complexes Bearing Carboxylate
Synthesis, Spectral Characterization and Electrochemical Properties of New vic-dioxime Complexes Bearing Carboxylate
复制标题
新型含羧酸盐的维二肟配合物的合成、光谱表征及电化学性能
DOI：
10.1007/s11243-006-0043-z
复制
发表时间：
2006
影响因子：
1.7
通讯作者：
I. Yilmaz
中科院分区：
文献类型：
--
作者：
A. Kilic;E. Taş;B. Gumgum;I. Yilmaz
首次合成了三个新的邻二肟配体[N-（乙基-4-氨基-1-哌啶甲酸酯）-苯基乙二肟（L1 H2），N-（乙基-4-氨基-1-哌啶甲酸酯）-乙二肟（L2 H2），N，N′-双（乙基-4-氨基-1-哌啶甲酸酯）-乙二肟（L3 H2）]及其Co（II）与Cu（II）金属配合物。用Co（II）和Cu（II）盐制备了这些配体的具有1：2金属-配体比的单金属配合物。合成了BF ~（2+）封端的Co（II）和thevic-dioxime单核配合物[Co（L_1·BF ~（2））_2]和[Co（L_2·BF ~（2））_2]。配体在碱存在下通过氮原子以多齿方式键合，如mostvic-二肟。钴（II）和铜（II）络合物是非电解质，如它们在DMF中的摩尔电导率（ΛM）所示。配体和配合物的结构通过元素分析、FT-i.r.紫外-维斯光，1H-和13C-n.m.r.光谱、磁化率测量和摩尔电导率。比较电化学研究表明，肟基上的取代基对配合物的氧化态和还原态的稳定性及电极电位均有影响。
Three newvic-dioxime ligands, [N-(ethyl-4-amino-1-piperidine carboxylate)-phenylglyoxime (L1H2),N-(ethyl-4-amino-1-piperidine carboxylate)-glyoxime (L2H2), andN,N′-bis(ethyl-4-amino-1-piperidine carboxylate)-glyoxime (L3H2)], and their Co(II) with Cu(II) metal complexes, were synthesized for the first time. Mononuclear complexes of these ligands with a 1:2 metal-ligand ratio were prepared with Co(II) and Cu(II) salts. The BF2+-capped Co(II) and mononuclear complexes of thevic-dioxime were prepared for [Co(L1·BF2)2] and [Co(L2·BF2)2]. The ligands act in a polydentate fashion bonding through nitrogen atoms in the presence of a base, as do mostvic-dioximes. The cobalt(II) and copper(II) complexes are non-electrolytes as shown by their molar conductivities (ΛM) in DMF. The structures of the ligands and complexes were determined by elemental analyses, FT-i.r., u.v.–vis.,1H- and13C-n.m.r. spectra, magnetic susceptibility measurements, and molar conductivity. The comparative electrochemical studies show that the stabilities of the reduced or oxidized species and the electrode potentials of the complexes are affected by the substituents attached on the oxime moieties of the complexes.