四种含苯并咪唑基双核Cu(Ⅰ)配合物的合成、表征和氧合性能  

Syntheses, Characterization and Oxygenation Properties of Four Benzimidazolyl-containing Dicopper(Ⅰ) Complexes

作　　者：李晓燕[1] 孙宏建[1] 孙东方 

机构地区：[1]山东大学化学系,济南250100

出　　处：《化学学报》1995年第4期336-342,共7页Acta Chimica Sinica

基　　金：国家自然科学青年基金资助课题.

摘　　要：本文合成了四种具苯并咪唑基配体；邻－二（２′－苯并咪唑甲基）氨基）－反式－环己烷（ＯＣＴＢ）及其三种系列物，分别与Ｃｕ（ＣＨ３ＣＮ）４ＣｌＯ４反应制得了相应的双核Ｃｕ（Ｉ）配合物１～４，经元素分析，红外光谱和核磁共振等表明自由配体及相应配合物元首会合组成。紫外－可见光谱表明配配物１～４具有氧合性能，它们的无色ＤＭＦ溶液吸氧后呈绿色，在可见区７００ｎｍ附近出现宽吸收峰，用抗坏血酸还原成无色。This paper reports the syntheses of four benzimidazolyl-containing ligands: ortho-bis [N, N'-bis(2'-benzimidazolyl-methyl) amino]-trans-cyclohexane (OCTB) and its three alkyl-substituted derivatives. Dicopper(I ) complexes 1-4 were respectively prepared through the reactions of the ligands with [Cu(CH3CN)4]ClO4. Elemental analyses, IR spectra and 1H NMR show that the compositions of the ligands and the complexes are the same as desired. UV-vis spectra indicate that complexes 1-4 can combine with dioxygen. The colorless solutions of the complexes in DMF show an uptake of oxygen and give green solutions with a wide absorption peak about at 700 nm. Addition of ascorbic acid (AA) results in decolorization of the solutions and the cycle can be repeated three or four times. Equilibrium constants, ΔH° and ΔS° of oxygenation reactions of the complexes in DMF are obtained by manometric oxygen-uptake measurements. We consider that the steric hindrance on N atom of benzimidazole is unfavourable to oxygenation. The electron-donating substituents on N atom would increase the electron density of coordination atom and further the central ion Cu(I ) and make the oxygenation more easier. The oxygenation rates in different solvents are in the order of DMF>DMSO>Py.

关 键 词：双核配合物 氧载体 血蓝蛋白 铜 苯并咪唑 

分 类 号：O614.121[理学—无机化学] O626.23[理学—化学]