配基

The auxiliary can be recovered in high yield (81%) only by filtering and recrystallization. Besides, some other aldehydes have been chosen to test the enantioselectivity of N,N\'-dibenzyl tartamide, in comparison with two other allylaborates reagents developed previously by Roush and Brown, respectively. The results show that %e.e. of homoallylic alcohol is superior to that of the former, and approaches the Brown reagent.

产物经S_N2反应得瑞格列萘中间体-甲基烯丙基-2-氯苯基-叠氮甲烷(17)；同时，将筛选出的新型手性配体N-苄基酒石酸二酰胺用于其他几种醛(正丁醛，异戊醛和环己醛)的不对称烯丙基化反应，并与广泛应用的Roush配体(22)和Brown配体(27)相比较，发现其立体选择性优于Roush配体，并接近Brown配体，但明显具有可回收利用的优势。

Part 7 is the conclusion of this paper.The main research in this paper includes:1 The 22 mixed ligand complexes were synthesized in which bipyridine-, phenanthroline 5-nitrophenanthroline , phenanthroline- 5,6-dikentone and biquinoline are the first ligand and chlorine ion phenylalanine, tyosine asparagic radical 2.6-diaminocaproic radical tryptophan , histidine malonate(mal2-) benzyl malonate (bmal2-) phenethtyl malonate (pmal2-) are the second ligand.

本文具体研究内容包括四部分：一、合成了以联吡啶、邻菲啰啉、5—硝基邻菲啰啉、邻菲啰啉-5，6-二酮、联喹啉为第一配体，以Cl~-、苯丙氨酸根、酪氨酸根、天冬氨酸根asp~(2-、赖氨酸根、色氨酸根、组氨酸根、丙二酸根mal~(2-、苄基丙二酸根bmal~(2-和苯乙基丙二酸根pmal~(2-为第二配体的共22个混配配合物，制备了其中6个混配配合物和1个单配体配合物单晶，用X-射线单晶衍射法测定了晶体结构。

A series of novel chiral aminophosphine ligands with binaphthyl backbone and partially reduced binaphthyl backbone were synthesized from optically pure NOBIN and H〓-NOBIN respectively. The effects of binaphthyl backbone and substitutes at the phosphorous atom on Pd (0)-catalyzed allylation of racemic 1, 3-dipheylprop-2-en-1-yl acetate with dimethyl malonate were systematically investigated.

从NOBIN出发合成了一系列膦上含有不同取代基的氮膦配体MAPs以及含有被部分还原的联萘骨架的氮膦配体H〓-MAPs，将此两类配体运用于钯催化的乙酸1，3-二苯基烯丙基酯与丙二酸二甲酯的反应中，考查了膦上取代基和配体骨架对反应的影响。

Four new salicylaldehyde derivatives with a glucose or mannose moiety were synthesized with 2-tert-butylphenol or 4-tert-butylphenol as the starting material, followed by the formylation, chloromethylation, nucleophilic substitution reaction with the desired carbohydrate. The salicylaldehyde derivatives condensed with ethylenediamine to give the Schiff bases, which coordinated with Mn to afford four novel sugar-based Salen Mn complexes.

首先，分别以2-叔丁基苯酚和4-叔丁基苯酚为起始原料，经过甲酰化反应、氯甲基化反应、和糖类衍生物的亲核取代反应制得了四种新型并入葡萄糖基或甘露糖基的水杨醛衍生物，将它们与乙二胺缩合生成希夫碱配体，得到的配体与过渡金属Mn~(3+)配位制备出四种新型含糖基的Salen Mn配合物。

In this thesis, a series of complexes based on aromatic multicarboxylic acids have been successfully synthesized in solutions or under hydrothermal conditions. Their structure and properties are investigated.(1) Eight complex compounds have been synthesized and characterized by X-ray single crystal diffractive technology: The eight complexes are listed as following: [Cu242] complex 1 [Cd22(H2O)4]·4H2O complex 2 [Co(H2btc)(H2O)3] complex 3 [Co2(H2O)2]·H2O complex 4 [Ni22(H2O)4] complex 5 [Cu22(H2O)4] complex 6 [Co(H2biim)2(H2O)2](H2btc) complex 7 [Zn(H2biim)2(H2O)2](H2btc) complex 8 The structure of complex 1 is dinuclear complex resulted from weak interactions（0-D chain）; complex 2 is 1-D chain stucture result from interactions of water molecules; complex 3、4、5、6 are coordination polymers using hydrothermal synthses, where the first kind ligand is H4btc, the second kind ligand is phen and Co2+、Ni2+、Cu2+ as center ions, respectively. While the coordination enviroment of Co2+ is the same in complex 3, the coordination geometries around the Co atoms in complex 4 are obviously different because of the different reaction conditions. In complex 4, the 1-D chains are connected into 2-D layer through carboxy groups of ligand H4btc. The structures of complex 5、6 are 1-D chain stucture result from interactions of carboxy groups in ligand H4btc. Complex 7、8 are homeomorphy compounds. Either of them are linked to the 3-D chains through intermolecular hydrogen bonds. Each H4btc lose two protons and H2btc2- acts as negative electron balance.

合成了8个结构新颖的配合物，并用X-射线单晶结构分析方法确定了晶体结构，分别为： [Cu242] 配合物1 [Cd22(H2O)4]·4H2O 配合物2 [Co(H2btc)(H2O)3] 配合物3 [Co2(H2O)2]·H2O 配合物4 [Ni22(H2O)4] 配合物5 [Cu22(H2O)4] 配合物6 [Co(H2biim)2(H2O)2](H2btc)配合物7 [Zn(H2biim)2(H2O)2](H2btc)配合物8 配合物1是一个依靠弱作用连接的双核铜结构；配合物2借助水分子形成一维链状结构；配合物3、4、5、6是以H4btc为第一配体、phen为第二配体，通过水热法合成的配合物，其中，Co2+、Ni2+、Cu2+为中心离子；配合物3中的二价钴离子具有相同的配位环境，不同反应条件下得到的配合物4中的二价钴离子存在不同的配位环境，在配合物4中，一维链通过H4btc上的羧基形成一个二维层结构；配合物5、6是借助H4btc上的羧基形成的一维链状结构；配合物7、8属于异质同晶结构，它们的分子通过分子间氢键形成三维网状结构，H4btc上的羧基失去2个质子，作为一个二价负离子起到电荷平衡作用。

From the structural analysis of three praseodymium complexes, we could draw a conclusion that as the dentate arms of carboxyl group on ligands elongating, the coordination numbers of Pr and the coordination modes of ligands increase, and the mean distances between metallic atoms of metallic helices existing in these complexes augment.2. By altering 5-substituting group of isophthalic acid three series of lanthanide complexes 8～19 with 5-methylisophthalic acid and 5-nitroisophthalic acid have been prepared.

从得到的三个配体的镨配合物的结构分析可以看出，随配体的羧基齿臂的增长，Pr的配位数逐渐增大，配体的配位模式增多，配合物中存在的螺旋金属链中的金属间平均距离增大。2、通过改变间苯二甲酸配体的5位取代基，制备了5-甲基间苯二甲酸和5-硝基间苯二甲酸的三个系列稀土羧酸配合物8～19。

In complexes 8～16 synthesized by hydrothermal method, most of the ligands adopt multidentate coordination modes joining several lanthanide ions into high-dimensional coordination polymers. And changing of 5-substituting group on isophthalic acid has a little effect on the coordinated abilities of the meta-carboxyl groups.

水热法制备的配合物8～16中，配体多采取多齿配位模式桥连多个稀土离子，形成高维配位聚合物，同时由于羧基氧原子和稀土离子的强的键合力，间苯二甲酸的5位取代基的变化对间位羧基的配位能力的影响不大。

Furthermore, the one-dimensional complexes 26 and 28 with strongπ-πpacking interactions are prepared from DMF solvent, which indicates that the traditional solvent volatilizing method could bring low-dimensional complex.4. By measuring the enthalpy changes of the liquid phase formation reaction for complexes a~e, and calculating the electronic densities of five 5-substituted derivation of isophthalic acid, we can make a conclusion that 5-substituted group changing of the ligand has a little influence on oxygen atoms of carboxyl groups.5. Fluorescence experiments of these complexes indicated that they could be used for luminescence materials in future.6. Using packing saturation rule we calculated and analyzed these series of complexes, and the results showed that the changes of complexes with changes of ligands could be explained from the rule.

在DMF溶剂中得到了具有强π-π堆积作用力的一维配位聚合物[Ln(5-NO_2-bdc)(NO_3)]Ln=Pr(26和Ho(28)，表明传统的溶剂挥发合成条件可以得到低维的配合物。4、通过配合物a～e的液相生成反应焓的测定，以及配体阳离子的电子密度计算，进一步佐证了间苯二甲酸的5位取代基变化对配体的羧基氧原子配位能力影响不大的结论。5、荧光特性表明此类配合物可以用于发光材料。6、利用堆积饱和规律对所得系列的配合物的进行计算和分析，发现随着配体的变化，配合物的变化可以从堆积饱和规律出发进行解释。

The first part is to synthesize 5-formyl -8- quinolinol from 8-uinolinol and chloroform , using ethanol as a solvent. Then analysizing the 5-formyl-8-quinolinol by IR. The second part is , according to ideas of molecule designing, to synthesize the new self-assembly Inorganic-Organic coordination polymers Co(u2-bpyV2O6,(C4H4N2)Ni2(H2O)2-V4Ol2,(Cl2Hl2N2)Co-V2O6 using Cu, Ni, and Co as templating, 4-cyano-pyridine(4-CNPy), 4,4-bipyridine,pyrazine, l,2-bis(4-pyridyl)ethane, 5-formyl -8- quinolinol as building blocks and Ammonium Metavanadate (NH4VO3) as subordinate building blocks by Hydrothermal , analysizing their content of element determining their structures by X-Ray diffraction.

本课题实验分为两部分：一是配体的合成，以8-羟基喹啉、三氯甲烷为原料，以乙醇为溶剂，合成了5—甲醛基—8羟基喹啉并且对其进行了IR的分析测定；二是配位聚合物的合成，通过分子设计，采用溶剂热法以Cu、Ni、Co为中心离子，以5—甲醛基—8羟基喹啉、4，4-联吡啶、吡嗪、1，2-二吡啶基乙烷为配体，以偏钒酸根(VO_3~-)为辅助配体，通过水热法自组装合成了新的3-D网状结构配位聚合物Co(μ_2-bpy)V_2O_6，(C_4H_4N_2)Ni_2(H_2O)_2·V_4O_(12)，C_(12H_(12)N_2Co·V_2O_6，并对其进行了元素分析和晶体结构的测定。

The complexing properties of compounds 10a, 10b, 11a and 11b toward alkali metal ions were studied by 〓H NMR titration, ESI-MS, UV-Vis spectra, Fluoresence spectra and liquid-liquid extraction. The results show:(1) the 1:1 complexes were formed.(2) The calix-crown 10a, 11a have a higher selectivity for Na〓 ions, whereas 10b, 11b for K〓 ions.(3) The complexing ability toward alkali metal ions was enhanced when the calix-crown have side arm carbonyl.(3) The coordination of alkali metal ions toward phenoxy, carbonyl and crown ethereal oxygens take place by rotation around the carbon-carbon bond of carbonyl and methylene.

六，用〓H NMR滴定，ESI-MS，UV-Vis，Fluorescence，液-液萃取实验研究了10a，10b，11a和11b对金属离子的配位性质，研究结果表明：1）杯芳烃冠醚衍生物同碱金属离子形成了1：1配合物，化合物10a、11a对Na〓具有较高的配位能力，化合物10b、11b对K〓具有较高的配位能力；2）在杯冠醚环的旁边引入带有羰基氧原子的基团作为侧臂参与配位可以加强对碱金属离子的配位能力；3）金属离子分别同苯酚氧，羰基氧，聚氧醚链氧发生了配位，配位过程中侧链基团涉及到了羰基碳与亚甲基碳的碳碳键的旋转过程。

According to the clear water experiment, aeration performance of the new equipment is good with high total oxygen transfer coefficient and oxygen utilization ratio.

曝气设备的动力效率在叶轮转速为120rpm～150rpm时取得最大值，此时氧利用率和充氧能力也具有较高值。

The environmental stability of that world - including its crushing pressures and icy darkness - means that some of its most famous inhabitants have survived for eons as evolutionary throwbacks, their bodies undergoing little change.

稳定的海底环境─包括能把人压扁的压力和冰冷的黑暗─意谓海底某些最知名的栖居生物已以演化返祖的样态活了万世，形体几无变化。