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本文合成了四种具苯并咪唑基配体:邻-二[N,N′-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~Ⅰ(CH_3CN)_4]ClO_4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其相应配合物均符合组成 紫外-可见光谱表明配合物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,如此可循环3～4次.用气体吸收测量方法算得配合物1～4于DMF中氧合反应平衡常数,△H~°和△S~°.研究表明,配体苯并咪唑N上空间位阻大不利于氧合;斥电性取代基可增加配位原子的电负性,使中心原子Cu(Ⅰ)上电子密度增加,有利于氧合.在不同溶剂中氧合速度大小为:DMF>DMSO>Py.
Four kinds of benzimidazolyl ligands were synthesized in this paper: ortho-bis [N, N’-bis (2’-benzimidazolylmethyl) amino] -trans-cyclohexane (OCTB) The corresponding binuclear Cu (Ⅰ) complexes 1 ~ 4 were obtained by reaction with [Cu ~ Ⅰ (CH_3CN) _4] ClO_4 respectively. Elemental analysis, IR and 1H NMR showed that the free ligands and their corresponding complexes In accordance with the composition of UV - Vis spectra showed that complexes 1 ~ 4 have oxygenation properties, their colorless DMF solution was oxygen after the green, visible in the vicinity of 700nm wide absorption peak, with ascorbic acid reduced to colorless, so can be recycled 3 ~ 4 times.The equilibrium constants of oxygenation of complexes 1 ~ 4 in DMF were calculated by gas absorption measurement, △ H ~ ° and △ S ~ ° .The results show that the spatial steric hindrance of the ligand benzimidazole N is not good Oxygenation; Rechargeable substituents can increase the electronegativity of the coordination atoms and increase the electron density on the central atom Cu (I), which is in favor of oxygenation.The rates of oxygenation in different solvents are: DMF> DMSO> Py .