大环多胺配体ODTH的合成及其性质的研究

A new dinucleating 36-membered octoazadiphenol macrocyclic ligand， 3，6，9，12，20，23，26，29-octoaza-35，36-dihydroxy-16，33-dimethyl-tricyclo-hexatriacontane-1(34)，14，16，18(36)，31，32-hexene， ODTH， was synthe-sized by NaBH4 hydrogenation of the corresponding Schiff base obtained from the [2+2] condensation between triethylenetetraamine and diformyl-p-cresol. It was characterized by elemental analysis， IR， UV-Vis， 1H NMR and MS. The protonation constants of ODTH and the stability constants of its complexes with Cu(Ⅱ) in 1∶1 and 1∶2 system(metal-ODTH)， have been determined potentiometrically at 25.0℃ and μ=0.100 mol·L^-1 KCl. Poten-tiometric equilibrium studies indicate that a variety of deprotonated and protonated mononuclear and dinuclear， as well as hydroxy-bridged complexes， form in the pH range 2～12 in aqueous solution. The species distributions and the characteristics of ODTH and the complexes are also described.     

两个新型的1，10-菲罗啉桥联多胺配体及其配合物的合成与热力学性质

合成了2个新型的多齿配体：2，9-二-[1′-（2″-苯并咪唑基）-2′-氮杂-正丙基]-1，10-菲罗啉(L₁)和2，9-二-[2′-（2″-苯并咪唑基）-3′-氮杂-正丁基]-1，10-菲罗啉(L₂)并且用元素分析和 ¹H NMR谱作了表征。在25 ± 0.1 ℃，运用pH电位滴定法对这2个新的配体及其与过渡金属离子M(Ⅱ)(M=Co，Ni，Cu，Zn)和稀土金属离子Ln(Ⅲ)(Ln=La，Nd，Sm，Eu，Gd)的配合物进行了热力学稳定性研究。结果表明配体和金属离子的配位比为1∶1，但是，这2个系列的配合物在稳定性方面存在很大差异。     

大环多胺及其金属配合物的研究新进展

论述了大环多胺及其金属配合物的合成应用研究进展,阐述了单核,双核及多核大环多胺的类型及其与金属的配合情况,全面地论述了该类化合物的超分子识别及其对核酸的切割作用,并讨论了其在金属配合物的荧光及其发光性能.     

芳香族磺酰胺型多齿配体及其双核金属配合物的合成（英文）

六种芳香族磺酰型多齿配体己由５－位取代的２－甲氧基－１,３－苯Ｍ醛和２－羟基１,３－苯二甲醛与Ｎ－（２－胶苯基）－对甲基苯磺酰胺作用合成。它们与铜（Ⅱ）、钴（Ⅱ）、镍（Ⅱ）盐作用生成双核配合物,后者用稀盐酸分解,得到５－位取代的２－羟基－１,３－苯二甲醛。     

西佛碱型大环多胺过渡金属配合物的合成与表征

西佛碱型大环多胺过渡金属配合物的合成与表征     

NEB与过渡金属元素二元配合物的pH电位法研究

用精密pH电位法测定了在甲醇 水混合溶剂中配体氨三乙氧基三苯甲酸 (NEB)质子化常数 (2 5℃ ,I =0 .2 0mol·L- 1 NaCl) ,讨论了溶剂对质子化常数的影响 ,结果表明溶剂对质子化常数的影响呈线性关系。测定了NEB与部分过渡金属M(Ⅱ) (M =Cd、Co、Ni、Cu及Zn)二元配合物的稳定常数 ,实验数据处理用程序MINIQUAD - 82和MIQUV完成。在二元体系中存在的配合物物种有 112、111、110及 2 10型 (M2 + ∶NEB3- ∶H+ ) ,并且 111及 110型配合物稳定常数的变化规律Cd(Ⅱ) Zn(Ⅱ)符合Irving Williams序列     

硫氮西夫碱配体及其金属配合物的合成与表征

合成了1，7－二（2′-苯甲酰）－1，4，7－三氧庚烷双缩肼基二硫以苄酯西夫碱配体及其Cu(Ⅱ），Ni(Ⅱ），Zn(Ⅱ）的配合物，并通过元素分析，IR和UV-vis对其进行了表征。     

不对称双膦配体及其Pt,Ni金属有机配合物的合成及其晶体和分子结构

本文提出了利用两步法合成烃基体积较大的对称和不对称1,2-二(二叔丁基膦)乙烷[d(t-Bu)pe]和1,2-二(苯基叔丁基膦)乙烷[Pb(t-Bu)pe]以及利用α,ω-双格氏试剂与PCl_3反应直接合成较大螯合环的1,4-二(磷杂环戊基)丁烷(dPCypb)和正丁基磷杂环戊烷[(n-Bu)(PCyp)]膦配体的新方法。并用通常的合成方法得到了这些配体的Pt,Ni金属有机配合物,其中[d(t-Bu)pe]PtCl_2,(dPCypb)PtCl_2,和[(n-Bu)(PCypP]PtCl_2,配合物进行了晶体和分子结构测定。讨论了配体的空间因素对配合物结构的影响。     

大环多胺及其金属配合物与DNA的相互作用

本文综述了近年来基于大环多胺及其金属配合物与DNA相互作用的研究进展,着重介绍本课题组在有关单双核、多核以及功能化大环多胺衍生物及其金属配合物与DNA相互作用方面的研究和发现,并对其在化学核酸酶方面的应用进行了讨论。在单双核大环多胺衍生物方面,我们分别合成了以吡啶、苯环、咪唑、三氮唑为侧臂的单核大环多胺金属配合物,同时合成了以刚性桥相连的双核配合物和以柔性链相连的双核配合物。并研究这些单双核大环多胺与DNA的相互作用,发现以刚性链相连的双核大环多胺金属配合物具有很好的切割DNA的性质,可以在低浓度、短时间内切断DNA。在功能化大环多胺方面,我们合成了含有碱基、PNA单体、咪唑鎓盐、冠醚、二茂铁等功能化基团的大环多胺衍生物及金属配合物,并研究了其与DNA的相互作用。在多核大环多胺方面,我们合成了基于大环多胺的寡聚物,研究发现该类物质可与DNA形成复合物,从而有效地保护DNA免于酶解。     

Thermal Analysis in Structural Characterization of Hydrazone Ligands and Their Complexes

Results of our research on synthesis and characterization of complexes with acylhydrazone derivatives are described in this review paper. Structural characterization of newly synthesized complexes by thermal analysis (TG, DTA, DSC) is particularly emphasized in this paper. Thermal analysis enabled us to study not only structural changes of substances during thermal treatment, but also the mode of coordination and degree of deprotonation of acylhydrazones, as well as geometry of the coordination sphere of complexes, the structure of which had not been determined by X-ray analysis. Topics in this paper are as follows: complexes of dioxomolybdenum(VI) with tridentate hydrazones, usnic acid derivatives and their Cu(II) complexes, as well as transition metal complexes with 2,6-diacetylpyridine bis(hydrazones). This revised version was published online in July 2006 with corrections to the Cover Date.     

双臂型方酰胺多齿配体的合成

自1959年发现方酸以来,已有许多文献报道其可以与多种金属离子,尤其是过渡金属离子形成配合物,但方酰胺多齿配体的研究却不多。在方酰胺内鎓盐中,二氧环丁烯具有电荷分离特性,其上的氧原子带部分负电荷,是理想的配体原子。如果以它为中心,对称地引入具有配位能力的分子片段,如甘醇     

Organotellurium Ligands & Their Metal Complexes: Recent Developments

Abstract

The ligand chemistry of telluroethers, halotellurium ligands, and polytellurides has received good attention in the last decade. Tellurium-containing species have been used to design clusters. In the recent past the ligation of di and tri-telluroethers (including bis(4-methoxyphenyltelluro)methane) has been studied. Hybrid organotellurium ligands, N-[2-(4-methoxyphenyltelluro)propyl]phthalimid (L ¹ ), 2-(4-ethoxyphenyltelluromethyl)-tetrahydro-2H-pyran (L ² ), 2-(2-{4-ethoxyphenyl} telluroethyl)-1,3-dioxane (L ³ ), N-{2-(4-methoxyphenyltelluro)ethyl}morpholine (L ⁴ ), N-{2-(4-methoxyphenyltelluro)ethyl}-pyrrolidine (L ⁵ ), bis{2-(pyrrolidine-N-yl)ethyl}telluride (L ⁶ ), 1-(4-methoxyphenyltelluro)-2-[3-(6-methyl-2-pyridyl) propoxy]ethane (L ⁷ ), and 2-[2-(4-methoxyphenyltelluro)ethyl]thiophene (L ⁸ ) have been designed recently and studied for their complexation reactions. The (Te, N) and (N, Te, N) ligands, L ⁵ and L ⁶ , coordinate with Hg(II) through Te and N both, but the bonding with N is some what weak. The morpholine nitrogen of L ⁴ does not coordinate with Pd(II) or Pt(II) along with Te. The L ⁷ behaving as a (Te, N) ligand has formed 20-membered metallomacrocycle ring with Pt(II). Tellurated Schiff bases 4-MeOC₆H₄TeCH₂CH₂N═C(CH₃)C₆H₄-2-OH (L ⁹ ) and 2-HO-C₆H₄-(CH₃)C═NCH₂CH₂TeCH₂CH₂N═C(CH₃)C₆H₄-2-OH (L ¹⁰ ) and their reduction products 4-MeOC₆H₄TeCH₂CH₂NHCH(CH₃)C₆H₄-2-OH (L ¹¹ ) and 2-HO-C₆H₄-(CH₃)CHNHCH₂CH₂TeCH₂CH₂NHCH(CH₃)C₆H₄-2-OH (L ¹² ) respectively have been synthesized and studied for ligation behaviour. The L ⁹ on reaction with the [Ru(p-cymene)Cl₂]₂ results in [Ru(p-cymene)(4-MeOC₆H₄TeCH₂CH₂NH₂)Cl]Cl · H₂O whereas in the reaction of L ¹⁰ with [Ru(p-cymene) Cl₂]₂, p-cymene ligand is lost resulting in [RuCl(L ¹⁰ -H)]. The recent developments, particularly designing of L ¹ to L ¹² and their ligand chemistry, are reviewed in the present paper.     

Hydrothermal Synthesis of Three New Transition Metal Complexes with Azido Ligands

Hydrothermal reactions of NaN₃, 1, 10‐phenanthroline or 2, 2′‐bipyridine and transition metal cations including Zn^II or Co^II in basified aqueous solutions yielded the three complexes, [Zn₂(bipy)₂(N₃)₄]_n ( 1 ), [Zn(phen)(N₃)₂]_n ( 2 ), and [Co(phen)₂(N₃)₂] ( 3 ), which were characterized by X‐ray crystallography. All three complexes crystallize in the triclinic system, space group P1¯, with a = 6.5506(2), b = 10.8441(6), c = 16.893(2)Å, α = 96.333(5), β = 95.361(7), γ = 90.548(6)° for 1 ; a = 7.0302(10), b = 10.0590(14), c = 10.4550(15)Å, α = 109.372(2), β = 103.980(2), γ = 106.137(2)° for 2 ; and a = 8.1722(2), b = 11.0332(3), c = 12.5066(2)Å, α = 82.681(8), β = 82.457(9), γ = 72.991(7)° for 3 , respectively. The photoluminescence spectra for compounds 1 and 2 have also been studied.     

Metal Complexes Bearing Terminal Borylene Ligands

More and more metal complexes with terminal borylene ligands will be synthesized. Although these ligands in metal complexes must be stabilized either by integration of the boron atom into a polyhedral skeleton ( 1 ) or by B–N π interactions with a bulky amino group ( 2 ), the route to new complexes with terminal RB ligands (R=alkyl, aryl) is clearly indicated.     

Multidentate Acyclic Neutral Ligands and Their Complexation

The properties of cyclic crown ethers are approximated by acyclic neutral ligands (popdands), which are compared and contrasted with open-chain bioionophores and acidic chelating agents in this article. Variations of the endo-polarophilicity/exo-lipophilicity balance, complex stability, ion slectivity can often be accomplished more easily, with greater versatility, and at less expense with acyclic polyethers than with their cyclic counterparts; complexation and decomplexation are generally faster in acyclic systems; and the pseudocavity usually has greater conformational flexibility. Acyclic crown ethers and open-chain cryptands stiffened by rigid “terminal groups” containing donor atoms readily form crystalline complexes of alkali and alkaline earth metals. Some oppen-chain neutral ligands form helical conformations in their crycstalin complexes. The observed coordination numbers and geometries are of theoretical interst. Attractive terminal group interactions lead to pseudocyclic species occupying a position intermediate between cyclic and acyclic ligands. It has recently proved possible to isolate crystalline complexes of alkali and alkaline earth metal ions with weakly donating oligo(ethylene glycol ethers) and with glycols; such complexes have also been obtained with sugars. Acyclic neutral ligands can serve as simple models of nigericin-type bioionophores and be used analytically in microelectrodes. The recently discoverd crystalline stoichiometric complexes formed by some acyclic neutral ligands with guest molecules such as urea, thiourea, and water provide a fresh insight into weak interactions between neutral molecules and for the development of urea receptors.     

联三吡啶配体组装及其金属络合物性能*

金属-配体间的配位作用是超分子化学中最重要的相互作用之一,寡聚吡啶配体可以与许多过渡金属离子配位,形成具有独特磁、光物理和电化学性质的过渡金属配合物,因此联三吡啶配体过渡金属配合物性能研究引起化学家的广泛关注。本文系统综述了联三吡啶配体及其衍生物的组装策略及其过渡金属配合物的光化学与光物理性能,包括单极、二极及多极配体以及由这类配体组装得到的各种拓扑结构的单核、多核过渡金属配合物,如线型金属寡聚物、金属聚合物、金属大环化合物、有机金属树枝状化合物等,并介绍这些配合物在该领域研究和应用前景。     

磺酰胺型多齿配体的合成

有机金属配合物涉及了许多重要的生命过程,配体和配合物的合成及性质研究都越来越受到人们的重视。磺酰胺类化合物,磺酰胺中氨基氢的酸性可与酚类化合物相比拟,对金属离子有较强的配位能力,并且比酚试剂不易氧化,还可改变磺酰胺的空间体积和亲脂性。本文报道一类新的磺酰胺型多齿配体的合成,并证明它们能与金属离子形成配合物。