Synthesis, Characterization and Crystal Structure of Quaternary Complex of Gadolinium （Ⅲ）

Ａｎｕｍｂｅｒｏｆｌａｎｔｈａｎｉｄｅｔｅｒｎａｒｙｃｏｍｐｌｅｘｅｓｃｏｎ ｔａｉｎｉｎｇｈｅｔｅｒｏｃｙｃｌｉｃａｍｉｎｅｓｈａｖｅｂｅｅｎｒｅｐｏｒｔｅｄｓｉｎｃｅ1960 [1] .Ｉｎｒｅｃｅｎｔｙｅａｒｓｍｕｃｈａｔｔｅｎｔｉｏｎｈａｓｂｅｅｎｐａｉｄｔｏｑｕａｔｅｒｎａｒｙｃｏｍｐｌｅｘｅｓｏｆｌａｎｔｈａｎｉｄｅｓｂｅｃａｕｓｅｏｆｉｎ ｔｅｒｅｓｔｉｎｇｓｔｒｕｃｔｕｒｅ ,ｃｏｏｒｄｉｎａｔｉｏｎｍｏｄｅ ,ｃｏｍｐｅｔｉｔｉｏｎｒｅ ａｃｔｉｏｎａｎｄｐｒｏｐｅｒｔｙ[2～ 9] .ＥＳＲｃａｎｅ…     

New N,O-containing ligands for the biomimetic copper-catalyzed polymerization of 2,6-dimethylphenol

Poly(2,6-dimethyl-1,4-phenylene ether) (PPE), which is widely used in high-performance engineering plastics, is obtained by the copper-catalyzed oxidative coupling of 2,6-dimethylphenol. The oxidative polymerizations have been carried out in acetonitrile with structurally related [copper-(N,O-containing ligand)] complexes as the catalyst precursor compounds, which appeared to be of great interest for a better understanding of the factors influencing the catalytic activities. Steric effects (influence of a methyl group close to the metal center; ligands 4–7) or electronic effects (imino versus amino group; ligands 4, 5, 8 and 6, 7, 9, respectively) on the polymerization rates have been demonstrated. The use of mono- or dinucleating ligands has strengthened the proposed mechanism of the reaction involving dinuclear active species.     

Synthesis and characterization of soluble (porphyrinato)iron(II) polymers

The use of (tetrakis(4-hexylphenyl)porphyrinato)Fe(II) in polymerization reactions with bidentate ligands such as 9,10-diisocyanoanthracene and 1,4-diisocyanobenzene led to well-defined stacked polymers1 and2 which are still soluble in common organic solvents such as chloroform, dichloromethane, and tetrahydrofurane. They have been completely characterized by¹H-NMR and UV/vis spectropscopy in solution, even allowing end-group analysis for determination of the average degree of polymerization, yieldingn=10 andn=5 for1 and2, respectively. Mößbauer and IR spectroscopy further established the strong Fe-CN bonding reflected by very small isomer shifts and quadrupole splittings (E _Q0.2 mm s^–1) and a large decrease in the IR stretching frequency (v _CN60 cm^–1). The axially stacked polymers exhibit semiconducting properties only upon doping.Presented at the 5th International Symposium on Macromolecule-Metal Complexes (MMV), Summer 1993 in Bremen, Germany.     

Polymer pendant ligand chemistry, 4. Recovery of precious metal ions from strongly acidic solution with a polymer-supported o-phenylenediamine hydrochloride ligand

We report on the synthesis and reactivity of a polymer-supported o-phenylenediamine hydrochloride ligand, PS-PDHC, using macroporous 6% crosslinked polystyrene-divinylbenzene beads. The PS-PDHC ligand was found to be highly selective to AuCl₄⁻ ions in strongly acidic solutions in the presence of other precious metal ions, PdCl₄²⁻, PtCl₄²⁻, RhCl₆³⁻, and RuCl₅²⁻ (selectivity values: 2.5, Au/Pd; 7.5, Au/Pt; 7, Au/Rh; 2.2, Au/Ru) as well as other transition metal ions, Fe ³⁺, Cr³⁺, CU²⁺, Nit+, and Mn²⁺. The sorption capacity, selectivity, kinetics of removal and recovery, and solution isotherms have been determined for AuCl₄⁻ ions in competition with the above-mentioned metal ions. The relative ease of formation of the anionic complex in 0.5 M HCI, AuCl₄⁻ was thought to be the primary reason for its selective ability to bind to the PS-PDHC ligand by an anion-exchange mechanism. Therefore, the effect of the HCI concentration on the kinetics of AuCl₄⁻ ion removal from solution was also investigated to clearly show that raising the pH from 0 to 5 caused a dramatic decrease in rate. The AuCl₄⁻ ion can be recovered quantitatively from the PS-PDHC beads using a 5% thiourea solution in 0.1 M HCl, allowing the polymer-supported ligand to be reused.     

Hydroformylation of functional alkenes with heterodonor phosphine rhodium catalysts: substrate or ligand directed regioselectivity?

The catalytic activity and selectivity of heterodonor phosphine rhodium catalysts prepared in situ were tested in the hydroformylation of functional alkenes (ethyl acrylate, methyl methacrylate, styrene, 4-vinyl-1-cyclohexene, dicyclopentadiene and cis-1,2,3,6-tetrahydrophthalic anhydride). Systematic variation of the heterodonor atom in the ortho position of the ligand showed that the heterodonor atom has a significant influence on the activities and selectivities of the reaction. However, the activity seems to depend mainly on the modifying ligand, and the regioselectivity mainly on the substrate (i.e., the structure and functionality of the alkene). Nevertheless, regioselective control is only obtained through synergy between the substrate and the catalyst. Clear regiocontrol was observed in the hydroformylation of ,-unsaturated esters and styrene with an in situ formed o-(thiomethylphenyl)diphenylphosphine rhodium catalyst.     

Ligand Design in Atomically Precise Copper Nanoclusters and Their Application in Electrocatalytic Reactions

Metal nanoclusters (MNCs) are compositionally well-defined and also structurally precise materials with unique molecule-like properties and discrete electronic energy levels. Atomically precise ligand-protected Cu nanoclusters (LP-CuNCs) are one category of typical MNCs that usually demonstrate unique geometric and electronic structures to serve as electrocatalysts. However, the synthesis, application, as well as structure-performance relationship of LP-CuNCs are not adequately studied. Significantly, the ligands are essential to the geometric structure, crystal structure, size, and electronic structure of LP-CuNCs, which determine their physiochemical properties and applications. In this review, significant progress in the ligand design of LP-CuNCs, and their application in electrocatalytic reactions is introduced. The general basics of ligand-protected MNCs (LP-MNCs) are first introduced and the functions of ligands are emphasized. Subsequently, a series of different ligands for LP-CuNCs including thiolates, phosphines, alkynyl, polymers, and biomolecules are highlighted. Thereafter, their applications in different electrocatalytic reactions are discussed. It is believed that this review will not only inspire the design and synthesis of novel LP-CuNCs, but also contribute to the extension of their applications in electrocatalytic reactions and the establishment of accurate structure-performance relationships.     

基于Ⅳ-Ⅵ族化合物的胶体量子点太阳电池研究进展

基于Ⅳ-Ⅵ族化合物的胶体量子点具有易于合成、带隙可调等优点,被认为是一种非常有前途的窄带隙光伏材料。近年来,利用Ⅳ-Ⅵ族化合物制作的胶体量子点太阳电池最高转换效率已经突破10%。介绍了胶体量子点的合成方法、基本结构及其光电特性;着重分析了国内外关于肖特基和异质结胶体量子点太阳电池的研究现状,指出了目前该领域研究中存在的问题和发展趋势,并分析了未来需要重点解决的关键问题。     

共聚物配体钌配合物的苯环催化加氢性能研究

采用XPS等分析手段证实了2-乙烯基吡啶和甲基丙烯酸乙二醇双醋的交联共聚物小球可作为配体与钌形成配合物,该配合经硼氢化钠还原后生成加氢催化剂PVMRu*,其对苯环(苯、苯酚)催化剂加氢的性能良好,所生成产物的选择性高.实验结果表明:温度、压力及搅拌速度的提高均有利于提高反应的活性.     

几种膦铑络合物及其MAC络合物的量子化学计算

采用从头计算方法(HF)对几种膦铑络合物[Rh(R，R)-DIPAMP]^ ，[Rh(S，S)-CHIRAPHOS]^ ，[Rh(DIPHOS)]^ 及它们与乙基-α-乙酰胺基肉桂酸(MAC)结合形成的中间体[Rh(R，R-DIPAMP)(MAC)]^ ，[Rh(S，S-CHIRAPHOS)(MAC)]^ ，[Rh(DIPHOS)(MAC)]^ 的几何结构进行了优化，计算结果显示：(1)采用从头计算方法对含有膦铑络合物的较大催化体系的全优化计算是可行的；(2)分子构型不同的双膦配体及其所形成的膦铑络合物中大部分主要原子间的键长、键角数据相差不大，但手性的不同对膦铑络合物的部分键长、键角数据有所影响；(3)在与(MAC)形成络合物前后，双膦配体上主要原子的电荷分布变化并不显著，但金属铑原子上的电荷则显著增加，可能是MAC在与膦铑配体络合过程中有电荷向铑原子上进行了转移．