锌(Ⅱ)-12-正戊基-1,4,7,10-四氮杂环十三烷-11,13二酮-α-氨基酸三元配合物的稳定性

合成了一种新的双氧四胺大环配体：12-正戊基-1,4,7,10-四氮杂环十三烷-11,13二酮(L)。采用pH电位法,在(25±0.1)℃,I=0.1mol·dm^-^3NaNO~3条件下,测定了锌(Ⅱ)与L的二元配合物及锌(Ⅱ)与L和六种α-氨基酸(AA=Gly,Ala,Val,Leu,Ile,Phe)形成的三元配合物的稳定常数。结合量子化学计算结果,讨论了在双氧四胺大环配体上引入疏水碳链形成具有双亲结构的配体后,与金属离子的配位能力的变化以及形成Zn(L)(AA)三元配合物稳定性变化规律。     

配位化学中的直线自由能关系 ⅩⅫ.铜(Ⅱ)—α-氨基酸—二氧四胺大环三元体系

用pH法在25.0+0.1℃,I=0.1mol·dm~(-3)KNO_3条件下研究了铜(Ⅱ)—α-氨基酸—13-(2′-羟基-3′,5′-取代苄基)-l,4,8,11-四氮杂环十四烷-12,14-二酮竞争性三元混配型配合物的稳定性.测定了该体系的三元配合物的稳定常数,并讨论了二氧四胺大环配体的环空腔大小对三元配合物的构型及稳定性的影响以及大环配体上取代基对三元配合物的影响     

配位化学中的直线自由能关系XXII: 铜(II)-α-氨基酸-二氧四胺大环三元体系

用pH法在25.0±0.1℃, I=0.1 mol.dm^-^3 KNO3条件下研究了铜(II)-α-氨基酸-13-(2'-羟基-3', 5'-取代苄基)-1, 4,8, 11-四氮杂环十四烷-12, 14-二酮竞争性三元混配型配合物的稳定性。测定了该体系的三元配合物的稳定常数, 并讨论了二氧四胺大环配体的环空腔大小对三元配合物的构型及稳定性的影响以及大环配体上取代基对三元配合物的影响。     

配位化学中的直线自由能关系XXII: 铜(II)-α-氨基酸-二氧四胺大环三元体系

用pH法在25.0±0.1℃, I=0.1 mol.dm^-^3 KNO3条件下研究了铜(II)-α-氨基酸-13-(2'-羟基-3', 5'-取代苄基)-1, 4,8, 11-四氮杂环十四烷-12, 14-二酮竞争性三元混配型配合物的稳定性。测定了该体系的三元配合物的稳定常数, 并讨论了二氧四胺大环配体的环空腔大小对三元配合物的构型及稳定性的影响以及大环配体上取代基对三元配合物的影响。     

配合物二水合-[N，N’双（2-苯胺基）乙二酰胺]合锌（Ⅱ）的荧光性质

二氧四胺大环配体是众多多胺中研究的一个重点,对此类配体形成的配合物的研究主要集中在培养单晶方面[1,2].近年来,对其荧光性质的研究已有报道[3,4].但用荧光分光光度法测定化合物的组成报道较少,本试验采用荧光分光光度法对配合物二水合-[N,N'-双(2-苯胺基)乙二酰胺](H2L)合锌(Ⅱ)(ZnL)的化学组成进行了研究,取得了较好的结果.     

C-取代二氧三胺大环配体合成及其Cu(Ⅱ)配合物性质研究

本文合成了1,4,7-三氮杂环十烷-8,10-二酮(td)和9-(2′-羟基苄基)-1,4,7-三氮杂环十烷-8,10-二酮(btd)两个新型二氧三胺大环配体,经元素分析,IR,1H NMR以及MS等方法表征.采用分子力学方法探讨了取代基对配体合成的影响.利用pH法,在25.0±0.1℃,Ⅰ=0.1mol/L KNO3条件下,测定了配体btd的质子化常数及其与Cu(Ⅱ)配位的平衡常数.结合光谱滴定及配合物EPR结果,讨论了二氧三胺大环配体与Cu(Ⅱ)离子的配位方式.     

6-(5＇-(8＇-羟基喹啉)亚甲基)-1,4,8,11-四氮杂十一烷-5,7-二酮·5-取代邻菲罗啉合铜(Ⅱ)-铜(Ⅱ)或钴(Ⅱ)双核混配体系的稳定性研究

本文合成了8-羟基喹啉取代的二氧四胺开链配体L并进行了红外、元素分析、核磁和质谱表征。在(25±0.1)℃,I=0.1mol·dm-3NaNO3条件下,运用pH电位滴定技术测定了双核混配体系Cu(Ⅱ)(或Co(Ⅱ)-L-5-取代邻菲罗啉合铜(Ⅱ)配合物的稳定常数,并从滴定数据、物种分布曲线和文献结果对配合物可能的配位方式进行了讨论。我们发现在Cu(Ⅱ)-L-5-取代邻菲罗啉体系的质子化过程中,开链二氧四胺与Cu(Ⅱ)存在微弱配位,而邻菲罗啉和8-羟基喹啉与过渡金属离子的结合力远大于开链二氧四胺,因此在金属离子与配体比合适的情况下能稳定存在双核或异双核配位化合物。在质子化过程中,直线自由能关系尚成立而在多核混配体系中,直线自由能关系不存在,这说明在如此复杂的体系中很可能存在有趣的配体-配合物-金属离子的协同作用。     

功能取代二氧四胺大环金属超分子配合物的溶液热力学性质研究

利用简单步骤合成了8-羟基喹啉取代的二氧四胺大环配体,此类配体含有两个独立的螯合基团,在适当情况下能分别与金属离子配位.在(25.0±0.1)℃,I=0.1mol/LNaNO₃条件下,用pH法测定了n(配体):n(金属离子)=2:3的二元配合物的稳定常数,并从滴定数据讨论了物种的可能构型.     

C-取代二氧三胺大环配体合成及其Cu(II)配合物性质研究

本文合成了1, 4, 7-三氮杂环十烷-8, 10-二酮(td)和9-(2'-羟基苄基)-1, 4, 7-三氮杂环十烷-8, 10-二酮(btd)两个新型二氧三胺大环配体, 经元素分析, IR, 1H NMR以及MS等方法表征。采用分子力学方法探讨了取代基对配体合成的影响。利用pH法, 在25.0±0.1℃,I=0.1mol/L KNO3条件下, 测定了配体btd的质子化常数及其与Cu(II)配位的平衡常数。结合光谱滴定及配合物EPR结果, 讨论了二氧三胺大环配体与Cu(II)离子的配位方式。     

D-π-A型吡啶锌配合物的合成、晶体结构及光性质(英文)

一种新型的D-π-A型吡啶配体L(L=反式-4-[4′-(N-甲基-N-羟乙基)胺]乙烯基吡啶)与卤化锌反应,合成了3种配合物即ZnCl2L2(1),ZnBr2L2(2)和ZnI2L2(3)。其中配合物1和2通过X-射线单晶衍射的表征,分析结果表明这2种配合物中的锌原子都是四配位的,分别与配体中的2个氮原子和2个卤离子配位,而且锌原子形成的是畸变的四面体构型。在晶体中存在着许多弱作用力,包括氢键,π-π堆积等,这些都将影响他们的光致发光的性质。     

ⅡB族金属离子-5-取代邻菲罗啉-二酮肟配体三元体系的 稳定性研究

在(35±0.1)℃,I=0.1mol·dm^-^3KNO~3条件下,用pH法测定了二酮肟配体PnAO,5-取代邻菲罗啉(5-Rphen,R=CH~3,H,Cl,NO~2)的质子化常数,Zn(Ⅱ),Cd(Ⅱ),Hg(Ⅱ)分别与PnAO和5-Rphen二元体系的稳定常数,以及Zn(Ⅱ),Cd(Ⅱ),Hg(Ⅱ)-PnAO-5-Rphen三元体系的稳定常数。实验结果表明,在上述二元、三元体系中均存在良好的直线自由能关系,并从三元配合物构型上讨论了存在线性关系的内在原因。同时,讨论了金属离子、取代基对配合物稳定性的影响。     

铜(II)-5-取代邻菲啰啉-二氧四胺大环三元体系的稳定性研究

The stability of copper (Ⅱ)-13-(2'-Hydroxy-3',5'-substituted benzyl)-1,4,8,11-tetraazacyclotetradecane-12, 14-dione(RTADO-14) binary complex compounds and of copper (Ⅱ)-5-substituted-1,10-phenanthrolines(R'TADO)-RTADO-14 ternary complex compounds was studied by means of pH titration method at 25.0±0.1 ℃ and I=0.1mol?dm-3KNO3. The formation constants of binary and ternary complexes were obtained. The structures of the binary and ternary complxes and the effects fo substituents on macrocyclic ligands and on R'Phen were also discussed.     

钴(II)-联吡啶-α-氨基酸的热力学和动力学研究

关于联吡啶为第一配体的二元、三元配合物的热力学和动力学性质的研究,以铜（Ⅱ）作为中心离子最为多见,而以钴（Ⅱ）作为中心离子的报导较少．实验表明,过渡金属钻（Ⅱ）能与大多数的生物配体、大π共轭体系形成相当稳定的二元、三元配合物,是生物功能模拟的一个具有应用价值的中心离子·钴（Ⅱ）卟啉可以代替铁（Ⅱ）卟啉,模拟血红蛋白、肌红蛋白[1],在生物体内起到输送氧的作用．为了充分了解钴（Ⅱ）与生物配体的配伍能力、配位方式以及其配位过程的动态行为,为推动钴（Ⅱ）配合物及其生物功能的模拟研究,本文分别采用PH电位法…     

4-[(1,3-二氧代丁基)氨基]苯甲酸稀土配合物的合成、表征及发光性质

在乙醇体系中,由主配体4-[(1,3-二氧代丁基)氨基]苯甲酸(H2L,C11H11NO4)、稀土硝酸盐及辅助配体邻菲啰啉(phen)反应合成了两个系列8个配合物[Ln2(L)3(H2O)4]n(Ln=Sm(1),Eu(2),Tb(3),Dy(4));[Ln2(NO3)2(L)2(phen)2]n(Ln=Sm(5),Eu(6),Tb(7),Dy(8))。用元素分析、红外光谱、摩尔电导、热重分析进行表征,确定了产物的化学组成,推断了相应的结构。测定了室温时固体产物的激发和发射光谱,结果表明:由主辅配体共同配位的三元配合物的发光强度好于无辅助配体参与的二元配合物。测定了三元配合物的荧光寿命,其中铕和铽配合物显示较长的荧光寿命。     

Electrometric Studies on the Ternary Complexes of M(II) With Chlorpromazine and Some Amino Acids

 The stability constants for the binary M(II)- chlorpromazine hydrochloride (CPZ) and the ternary complexes M(II)-chlorpromazine-amino acid, have been studied using pH-measurements. The amino acids (aa) are: glycine, glutamic acid, histidine and the metal ions are: Cu(II), Zn(II), Co(II), Ni(II) and UO₂(II). All experiments were carried out in the presence of 0.1 mol dm⁻³ KNO₃. The resulting stability constants of the binary and the ternary complexes were compared. It was observed that the stability of the ternary complexes-except for glutamic acid – are lower than of the binary ones. Received October 22, 1998. Revision March 14, 1999.     

三元混配铂(Ⅱ)配合物的稳定性和分子内芳环堆积效应研究

用pH电位滴定法测定了铂(Ⅱ)与核苷酸NTP (NTP为腺苷5′-三磷酸和尿苷5′-三磷酸)和另一芳环系列配体ArL形成的三元混配配合物Pt(ArL)(NTP)n-(ArL=Phen, Bpy和Trp; n=2或3)在水溶液中的稳定常数(I=0.1 mol/L, KNO3; 25℃).用ΔlogKPt比较了二元和三元混配配合物的稳定性差异,认为三元混配配合物稳定性的增加可归因于π-酸与π-碱之间的合作效应和分子内芳环配体的堆积作用.     

The determination of the stability constants of mixed ligand complexes of adenine and amino acids with Ni(II) by potentiometric titration method

A potentiometric titration technique has been used to determine the stability constants for the various complexes of Ni(II) with adenine (A) as primary ligand and selected amino acids (L) as secondary ligands. Ternary complexes of amino acids are formed in a stepwise mechanism, whereby (A) binds to Ni(II), followed by interaction with ligand (L), whereas thiol-containing ligands form ternary complexes through a simultaneous mechanism. The formation constants of the complexes were determined at 25 °C and ionic strength 0.1 M NaNO₃. The relative stabilities of the ternary complexes are compared with those of the corresponding binary complexes in terms of Δlog K values. The concentration distribution of the complexes are evaluated.     

The effect of ligand donor atoms on ternary complex stability

Formation constants of mixed ligand complexes of Cu²⁺, Zn²⁺, Ni²⁺, Co²⁺, and Mn²⁺,with cyadine-5′-monophosphoric acid (CMP) and various primary ligands such as 1,10-phenanthroline(phen), glycylglycine(glygly) and salicylic acid (sal) have been determined in aqueous solution at 35°C and 0.1 M (KNO₃) by potentiomeric measurements. The acid dissociation constants of all the above mentioned ligands together with their 1 : 1 binary metal complex formation constants were also measured at 35°C. In general all the 1 : 1 binary complexes follow the Irving-Williams order of stability. Further the binary metal complexes of primary ligands are more stable than their ternary complexes with CMP. For ternary complexes, Δ(log K) values seem to change from positive to highly negative as the coordinating atoms of the primary ligands were varied from N,N to N,O^? to O^?O^?. The higher stability of ternary complexes involving phen is due to its Π-bonding interaction with the above metal ions and the relative decrease in the stability of other ternary systems is due to the coulombic repulsion of donor oxygen atoms of primary and secondary ligands. Thus for ternary complexes the stabilities follow a decreasing order of M-phen-CMP > M-glygly-CMP > M-sal-CMP.     

Studies of the Intramolecular Aromatic-ring Stacking Interactions in the Ternary Platinum(Ⅱ) Complexes

The stability constants of some ternary mixed-ligand complexes, Pt(Phen)(CA) , where Phen=1,10-phenanthroline and CA- =carboxylate, were determined by means of potentiometric pH titration in aqueous solutions(I=0.1 mol/L, KNO3; 25 ℃), and the stability of them was compared with that of the corresponding binary complexes. It was revealed that the ternary complexes containing phenylalkane carboxylates ligands(PCA-) are much more stable than those formed with formate and acetate. The results indicate that there exist the intramolecular aromatic-ring interactions between the phenanthroline ring of Phen and the phenyl moiety of ligand PCA- in the ternary mixed-ligand Pt(Phen)(PCA)- complexes. The extent of the stacking interactions, which depends on the number of methylene groups between the phenyl moieties and the coordinated phenylalkane carboxylate groups, was calculated. The best-fitted stack was obtained for the complexes with 2-phenylacetate and 3-phenylpropionate as the ligands.     

镍, 锌, 钴(II)-N-(间甲苯基)亚氨基二乙酸-氮三乙酸的量热研究

使用改进的RD-1型热导式量热计测量了镍(II), 锌(II),钴(II)-N-(间甲苯基)亚氨基二乙酸-氮三乙酸三元配合物的生成焓, 发现其大小按金属离子来说符合Irving-William序列。利用配体的多环水化结构等讨论了该三元配合物的生成焓和相应的二元配合物的生成焓, 同时求得了上述三元体系的热力学参数, 指出上述三元体系的生成熵是导致这些三元体系具有较大稳定性的根本原因。