共查询到19条相似文献,搜索用时 73 毫秒
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利用Sonogashira反应,以较高的产率将苯并-15-冠-5-基团修饰到铁氮化酶活性中心,得到了结构新颖的ADT型模型化合物1,电化学研究表明该化合物能够催化还原醋酸放出氮气,具有明显的产氢活性. 相似文献
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通过4,5-二溴甲基苯并-15-冠-5与2-萘酚和2-巯基苯并噻唑反应分别合成了两种新的双臂式苯并-15-冠-5(2和3),进而采用溶剂萃取的方法研究了它们与一些阳离子的键合行为.结果表明,冠醚2对碱金属钾离子和重金属铊离子表现出较高的选择性萃取能力,而冠醚3对重金属银离子表现出较高的选择性萃取能力. 相似文献
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Synthesis of Double-Armed Benzo-15-crown-5 and Their Complexation Thermodynamics with Alkali Cations
A series of double-armed benzo-15-crown-5 lariats (3–8) have been synthesized by the reaction of 4′, 5′-bis(bromomethyl)-benzo-15-crown-5 (2) with 4-hydroxybenzaldehyde, phenol, 4-chlorophenol, 4-methoxyphenol, 2-hydroxybenzaldehyde, and 4-acetamidophenol in 43 ~ 82% yields, respectively. The complex stability constants (K
S) and thermodynamic parameters for the stoichiometric 1:1 and/or 1:2 complexes of benzo-15-crown-5 1 and double-armed crown ethers 3–8 with alkali cations (Na+, K+, Rb+) have been determined in methanol–water (V/V=8:2) at 25 °C by means of microcalorimetric titrations. As compared with the parent benzo-15-crown-5 1, double-armed crown ethers 3–8 show unremarkable changes in the complex stability constants upon complexation with Na+, but present significantly enhanced binding ability toward cations larger than the crown cavity by the secondly sandwich complexation. Thermodynamically, the sandwich complexations of crown ethers 3-8 with cations are mostly enthalpy-driven processes accompanied with a moderate entropy loss. The binding ability and selectivity of cations by the double-armed crown ethers are discussed from the viewpoints of the electron density, additional binding site, softness, spatial arrangement, and especially the cooperative binding of two crown ether molecules toward one metal ion.Graphical Abstract Synthesis of Double-Armed Benzo-15-crown-5 and Their Complexation Thermodynamics with Alkali CationsYU LIU*, JIAN-RONG HAN, ZHONG-YU DUAN and HENG-YI ZHANG
This revised version was published online in July 2005 with a corrected issue number. 相似文献
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Six kinds of benzo-15-crown-5 (L) adducts having the stoichiometric formula M(Pic)2 · L · xH2O (M=Mn, Cu, x=2; M=Co, Ni, Zn, Cd, x=4; Pic means picrate anion) have been synthesized and characterized by EA, IR, UV and molar conductance. The X-ray crystal structural analysis of the benzo-15-crown-5 adduct with hydrated copper(II) picrate revealed that the benzo-15-crown-5 molecule virtually acts as a second-sphere ligand, which associates with the copper(II) ion by hydrogen bonding of the coordinating water molecule. By the comparison of the IR, UV spectra and molar conductance of the new adducts prepared, it can be deduced that the other adducts exhibit the similar coordination environment to that of the copper adduct. 相似文献