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Other than conventional concept, the N→Rh bond, formed by rhodium in the complex and nitrogen at pyridine ring in the ligand, did not break in the course of the carbonylation reaction, but formed into new active species instead, i.e., the ligand and rhodium as a whole participated in the oxidative addition of CH3I and the formation of CH3COI.

配合物中铑与吡啶环上共轭N形成的N→Rh配键,在羰基化反应过程中并非通常认为的断裂而是形成新的活性物种,即配体与铑作为整体参与了CH3I的氧化加成及CH3COI的生成过程。

The biological activities of the metal complexes of derivatives of benzaldehyde nitrogen mustard were investigated against 〓,〓 and SMMC-7721 cell lines. The interesting results were found. When the non-activity ligand combines with cobalt and nickel , the complexes have good antitumor activity, while active ligand binds to the metal, the complex has no activity, indicating there are synergic effect and counteraction between the metals and the ligands.

对所获得苯甲醛氮芥衍生物的金属配合物进行研究,观察它们对SMMC-7721、〓细胞株的作用,发现某些有趣的实验结果,无活性的配体,当与钴,镍形成配合物后,具有很好的抗肿瘤活性,而有活性的配体形成配合物后无活性,揭示在它们存在有协同作用及拮抗作用。

Mn-complexes in which Mn atom ligand with the N atom within ligand can stimulate the recovery of electron transfer and oxygen evolution. The trinuclear Mn-complex is extremely sensitive to the addition of CaCl2. It is suggested that there is an interaction between Ca2 and carboxyl within the trinuclear Mn-complex during photoactivation and this interaction benefits the ligation of Mn atom to the apo-WOC and form an active WOC. Binuclear MnMn complex shows slightly higher efficiency than binuclear MnMn complex in restoration of O2 evolution activity. It is suggested from our results that recovery of electron transport and O2 evolution with synthetic Mn-complexes is affected by different factors. Cl- can stimulate the reconstitution of WOC at the concentration of over 100mM;the maximal recovery of O2 evolution activity requires the presence of CaCl2 and 33 kDa protein polypeptide together. Bicarbonate can stimulate the reconstitution of WOC.

锰配合物中锰原子与配体中的氮原子配位连接时,能显著恢复电子传递活性和放氧活性;三核锰化合物在重组时对CaCl2的存在非常敏感,我们认为Ca2 与三核锰化合物中的羧基之间存在一定的相互作用,而这种作用有助于锰原子的光配位进而使三核锰化合物易于组装成有活性的水氧化复合物:双核锰化合物MnMn比双核锰化合物MnMn在恢复放氧活性方面更有效;影响锰化合物电子传递能力恢复的因素与影响锰化合物放氧活性恢复的因素不同;在锰蔟重组过程中,氯离子的浓度必须在100mM以上,才能有效进行光重组;最大光重组效率的获得必须有钙离子和33kDa多肽同时存在;碳酸氢根离子促进锰化合物与去锰光系统II的光组装。

In complex 1,Cucan be described as a four-coordinated square planar geometry.Compound 8 is the sodium salt of plumbagin and exists as ionic compound.Compounds 9-16 are the rare earth complexes of plumbagin with La,Y,Dy,Sm,Gd,Nd,Erand Eu.Compound 17 is binuclear Y complex.18 is mononuclear Ycomplex with plumbagin and another ligand from Plumbago Zeylanica.Compounds 19-21 are the ternary complexes with plumbagin and 2,2\'-bpy and phen as assistant ligand.In 19, the geometry of Cucan be described as five-coordinated distorted square pyramid that exists in a dimer through the weak bonding,and 1-D chain structure is formed by intermolecular hydrogen bonds.

化合物1的单晶结构分析表明1具有四配位平面四边形结构,化合物8是白花丹素的Na盐,以离子化合物形式存在;化合物9~16为白花丹素的La,Y,Dy,Sm,Gd,Nd,Er,Eu的稀土金属配合物;化合物17是白花丹素的双核钇结构;化合物18为白花丹素的单核钇结构,该配合物除了含白花丹素外,还有来自白花丹植物中的另一个单体化合物也参与配位;化合物19~21是以2,2\'-联吡啶和邻菲咯啉等含N配体为辅助配体,具有白花丹素—含N配体—金属离子的三元配合物,化合物19是白花丹素和2,2\'-联吡啶与Cu的配合物,具有五配位的四方锥构型,通过Cu…O弱的成键作用形成二聚体,再通过分子间的氢键作用进一步形成一维链状结构,化合物20和化合物21是白花丹素分别与2,2\'-联吡啶和邻菲咯啉的Zn配合物,都具有六配位八面体构型的双核锌配合物,呈一维链状结构,化合物20中链与链之间的大量氢键将一维链扩展成二维层,分子间的π-π堆积作用进一步形成三维结构。

The integrated analytical results show that the novel ligand coexists in ketoform and enolform structures under the measuring conditions, the ketoform structure may change into the enolform structure during the coordination and bonds with the central ion by two O atoms of the enolized hydroxyl group of pyrazolone ring and H2O and the N atom of the imine group and the N atom containing H of benzimidazole ring by losing the proton. And the coordination number of these complexes is four.

综合各种分析结果显示:配体在测试条件下以酮式和烯醇式结构共存,配位时酮式可能转化为烯醇式结构,按去质子的方式以吡唑啉酮环羟基和H2O上的两个O原子以及亚胺基上的N原子和苯并咪唑环上的含氢N原子与中心离子成键,配合物的配位数为4。

While associations consisted principally of zeolites not only can improve the reservoir performance for their diffluent properties, but also form lithological trap incorporated with sealing of areas without corrosion at the margin of sand body.

以浊沸石为主的沸石类自生矿物组合不但易溶能改善储集性能,而且与砂体边缘未被溶蚀区配合遮挡可组合成岩性圈闭。

Adjacent helical chains are racemic. The Ag atom is linked to two nitrogen atoms of the 2-pyridyl and 4'-pyridyl groups from two different 2,4'-bpy ligands as well as to the oxygen atom of the counterion. In 17 and 19, the adjacent helical chains are linked to wavy two-dimensional network structures by the nitrate counterions.

相邻的螺旋链间是外消旋的,Ag 原子与分别来自两个不同2,4'-联吡啶的2-吡啶基和4'-吡啶基的氮原子以及阴离子的氧原子配位,在配合物17和19中,相邻聚合螺旋链被硝酸根离子桥连接起来,变成了一个波浪形的二维网络结构;配合物18是首次通过无桥连配体支持的Ag ××× Ag键将相邻螺旋链连接成二维非穿插的网络结构。

According to Johnson's Rule and IR spectra, their possible structures are suggested. The bonding parameters of those complexes are calculated by ESR parameters. And the crystal field parameters are calculated by using electronic spectral data. It can be seen that the vanadyl complexes in the solution are ionic complexes and that the α〓 values of those complexes decrease following the increasing of the N donor replacing the O donor of water on the equatorial plane in those complexes. This means that the covalent bonding between vanadium and ligand increases as Ser, Phen or Bipy replace water ligands. The results show the competitive coordinate law that the coordination reactivity of Phen and Bipy is much stronger than that of Ser. The simulation program of ESR is compiled by the theory of ESR in the present work.

测定了VO-丝氨酸二元体系、VO-丝氨酸-邻菲咯啉三元体系和VO-丝氨酸联吡啶三元体系在不同酸度下(pH=1.0~14.0)的乙二醇/水(V/V=1:1)溶液低温ESR谱,发现不同pH下,溶液中具有不同组成的配合物,根据不同pH下ESR谱的变化,利用Johnson的加合规则并结合红外光谱,推测了它们在溶液中的可能结构;利用波谱参数计算了配合物键参数;利用电子光谱数据计算了配合物的晶体场参数,讨沦了它们的成配特性,结果表明:VO配合物属离子型配合物,随取代水分子的配体(Ser、Phen或Bipy)数目增加,键参数减小,配合物共价性增强,同时得出这些体系中,生物配体竞争配位规律:Phen和Bipy与VO的配位能力比Ser强。

Chiral ligands mentioned above and their complexes with acetate copper were used as enantio-selective catalysts in asymmetric cyclopropanation reactions of diazoacetate and 1,1-diphenyl ethylene. Investigations indicate that all of them reveal certain optical-selective capability, but chiral C2-symmetric 2,6-bispyridine ligands show better catalytic capability than chiral asymmetric schifF-base ligands.

选择了2个手性2,6-吡啶双噁唑啉配体和6个手性不对称席夫碱配体与醋酸铜形成的配合物作为催化剂,对重氮乙酸乙酯与1,1-二苯乙烯不对称环加成进行催化反应,发现这8个催化剂对1,1-二苯乙烯的不对称环丙烷化反应都表现出了一定的光学活性诱导能力,手性2,6-吡啶双噁唑啉-铜类具有比手性Schiff碱-铜类更好的催化性能。

In addition to cationic gold complexes bearing bulky biphenyl phosphines, a gold complex with tris(2,6-di-tert-butylphenyl)phosphite is exceptionally reactive as a catalyst for this reaction.

在与有大体积连苯基膦配体的金正配合离子加成反应中,三(2,6-二叔丁基苯)亚磷酸盐的金配合物异常活泼并充当该反应的催化剂

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