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It was found that this polymeric arsine palladium(0) complex is a highly active and stereoselective catalyst for arylation of styrene or acrylic acid.

通过用水合肼对上述聚硅氧烷负载的单齿胂钯配合物进行还原制备了聚硅氧烷负载的单齿胂钯(0)配合物,研究表明它是苯乙烯、丙烯酸芳基化反应的高活性和高立体选择性的催化剂。

New contributions of this work are as follows:(1). Preparation of Spherical MgCl_2-Supported Late-Transition Metal Catalysts for Ethylene PolymerizationFacile and effective immobilization of late-transition metal catalysts. 2,3-bis-(2,6-diisopropylphenyl) butane diimine nickel dibromide (1) and 2,6-bis-[1-(2,4,6-trimethylphenylimino)ethyl]pyridine iron dichloride (2), for ethylene polymerization has been achieved, using spherical MgCl_2 supports obtained by thermal dealcoholization of MgCl_2·2.56C_2H_5OH, and the effects of dealcoholization temperature on supported late-transition metal catalysts and the properties of resultant polymers were studied, the results indicated that:1.Supports with appropriate mechanical strength, high surface area and high porosity could be prepared by thermal dealcoholization of spherical MgCl_2·2.56C_2H_5OH supports; 2.BET, XRD, IR, SEM, GPC and DSC analyses indicate that the activities of the supported late-transition metal catalysts and the properties of resultant polymers are strongly dependent on the dealcoholization temperature.

本工作的新贡献如下:(1)、球形氯化镁负载后过渡金属催化荆催化乙烯聚合本文将配合物2,3-双(2,6-二异丙基苯亚胺)丁烷二溴化镍(1)和配合物2,6-二[1-(2,4,6-三甲基苯亚胺)乙基]吡啶二氯化铁(2)分别直接负载于经不同热脱醇温度处理的球形氯化镁载体上,研究了氯化镁载体的脱醇温度对负载化后过渡金属催化剂及其聚合物的影响,研究表明:1、通过对球形MgCl_2·2.56C_2H_5OH载体进行热脱醇处理,可以获得合适机械强度、较高比表面积和较高孔隙度的球形氯化镁载体;2、BET,XRD,IR,SEM,GPC和DSC研究表明,脱醇温度极大地影响负载后过渡金属催化剂的活性和聚合物的性能。

New contributions of this work are as follows:(1). Preparation of Spherical MgCl_2-Supported Late-Transition Metal Catalysts for Ethylene Polymerization Facile and effective immobilization of late-transition metal catalysts. 2,3-bis-(2,6-diisopropylphenyl) butane diimine nickel dibromide (1) and 2,6-bis-[1-(2,4,6-trimethylphenylimino)ethyl]pyridine iron dichloride (2), for ethylene polymerization has been achieved, using spherical MgCl_2 supports obtained by thermal dealcoholization of MgCl_2·2.56C_2H_5OH, and the effects of dealcoholization temperature on supported late-transition metal catalysts and the properties of resultant polymers were studied, the results indicated that: 1.Supports with appropriate mechanical strength, high surface area and high porosity could be prepared by thermal dealcoholization of spherical MgCl_2·2.56C_2H_5OH supports; 2.BET, XRD, IR, SEM, GPC and DSC analyses indicate that the activities of the supported late-transition metal catalysts and the properties of resultant polymers are strongly dependent on the dealcoholization temperature.

本工作的新贡献如下:(1)、球形氯化镁负载后过渡金属催化荆催化乙烯聚合本文将配合物2,3-双(2,6-二异丙基苯亚胺)丁烷二溴化镍(1)和配合物2,6-二[1-(2,4,6-三甲基苯亚胺)乙基]吡啶二氯化铁(2)分别直接负载于经不同热脱醇温度处理的球形氯化镁载体上,研究了氯化镁载体的脱醇温度对负载化后过渡金属催化剂及其聚合物的影响,研究表明: 1、通过对球形MgCl_2·2.56C_2H_5OH载体进行热脱醇处理,可以获得合适机械强度、较高比表面积和较高孔隙度的球形氯化镁载体; 2、BET,XRD,IR,SEM,GPC和DSC研究表明,脱醇温度极大地影响负载后过渡金属催化剂的活性和聚合物的性能。

The fluorescence properties of complexes of europium with β-diketone and terbium with benzoic acid and its derivatives were analyzed and the synergic effect of the second ligand was illustrated from the energy matching of the minimum triplet state of ligands and the resonance energy level of rare earth ions.

提出了掺杂离子荧光增强效应的机理。 4。首次采用ab initio CIS方法,在劈裂价层基组3—21G水平上对各配体进行了量化计算,系统分析了前线分子轨道特征和激发态的能级,从配体最低激发三重态能级与稀土离子共振能级的能级匹配,分析了铕与β-二酮的配合物的荧光性能和铽与苯甲酸系列衍生物的配合物的荧光性能,解释了第二配体的协同效应。

In all those complexes, no matter which conformation IDA assumes (mer- or fac-style), the two 0 atoms of 1N2O are both from carboxylic hydroxyl. However, by comparing the bond length, we can find that O(4) and O(2) atom is from different group in this complex, 0(4) atom from carboxylic hydroxyl, whereas, 0(2) from carboxylic carboxide.

值得注意的是:在这个双核配合物中,我们首次发现一种新颖的配位方式:IDA上与金属离子配位的三齿螯合原子是亚氨N原子、一个羧基上的羟基O原子和另外一个羧基上的羰基O原子。

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。

Reaction of 9-bromofluorenewith diethyl malonate and sodium carbonate gives diethyl 2-(9-Fluorenyl)malonate.Aminolysis of diethyl 2-(9-Fluorenyl)malonate in ethylenediamine and propylene diamine give〓 and 〓, respectively.〓 and 〓 were synthesized by the reaction of 9-bromofluorene with oxalyl bisethylenediamine. Copper and nickel complexes of 〓 and 〓 were obtained by the reaction of 〓 and 〓 with copper and nickel salt, respectively, in aqueoussolution and extrusion of two hydrogen ions from the amide groups.

使9-溴芴与丙二酸二乙酯在无水碳酸钠存在下反应合成出2-(9-芴基)丙二酸二乙酯。2-(9-芴基)丙二酸二乙酯在乙二胺中胺解得到配体〓,2-(9-芴基)丙二酸二乙酯在1,2-丙二胺中胺解得到配体〓,使9-溴芴与草酰二乙二胺作用得到配体〓和〓与相应的金属盐作用分别得到它们的铜、镍配合物。

Through condensing o-aminobenzoic acid, ethyl oxalyl chloride and ethylenediamine(or 1,2-propylenediamine), two new ligands N-benzoato-N′-(2- aminoethyl)oxamido(H3oxbe) and N-benzoato-N-(2-amino-2-methylethyl)oxamido(H3oxbt) have been synthesized. Their mononuclear complexes Na·1.5H2O and Na·1.5H2O have also been obtained.

2以邻氨基苯甲酸、草酸乙酯酰氯和乙二胺(或1,2-丙二胺)缩合制得了两种具有不对称草酰胺结构配体N-(2-苯甲酰基)-N&-(2-氨乙基)草酰胺(H3oxbe)和N-(2-苯甲酰基)-N&-(2-氨丙基)草酰胺(H3oxbt),并得到了它们的单核配合物:Na·1.5H2O和Na·1.5H2O。

The result indicated that MgO and α- methacrylic acid can together thicken epoxy, and the speed of thickening epoxy become quickly with the increasing content of MgO; when the ratio of MgO and α- methacrylic acid is 3:1, thickening epoxy have a better effect; the thickening mechanism: the terminal corboxyl group of α- methacrylic acid react with MgO, and it accompany with large numbers of heat, the heat can accelerate the reaction between the terminal corboxyl group with the secondary hydroxyl groups of epoxy, intermolecular hydrogen bonding which the water of above-mentioned formation result in and complex compound which format the metal atoms and carbonyl group complexing collective increase the viscosity of epoxy resin.

结果表明:MgO和α-甲基丙烯酸配合可增稠环氧树脂,随着MgO加入量的增加,环氧树脂增稠的速度加快;MgO与α-甲基丙烯酸为3:1时,增稠环氧树脂的效果较好;推测环氧树脂的增稠机理是α-甲基丙烯酸中的端羧基与氧化镁反应,放出热量促使其端羧基与环氧树脂中的仲羟基反应,上述反应生成水产生的氢键和羰基与氧化镁中的金属原子形成络合物共同导致环氧树脂的粘度增加。

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。

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