MOF-5负载Pd催化剂的制备及其催化性能初探

用水合肼还原Pd2+并将其负载在MOF-5上,制得了新型的Pd/MOF-5催化剂,采用XRD、氮吸附、SEM、TEM等多种手段对其进行了表征,催化剂的Pd纳米粒子尺寸在3~6nm之间。初步研究了该催化剂对催化卤代芳烃与芳基硼酸之间的Suzuki-Miyaura偶联反应的反应条件和催化性能,该催化体系具有反应条件温和、无需氮气保护和添加配体、产率优良等优点,催化剂循环利用5次仍然保持较高催化活性,平均产率超过90%。     

双(3-对甲苯基-2-硫代咪唑-1-基)-(3-甲基-5-苯基吡唑-1-基)硼氢酸根的镉及钴配合物的合成与结构表征

Two new complexes CdL₂ (1) and CoL₂ (2) were synthesized by reactions of L {L =hydro[bis(3-p-tolyl-2-thioimidazol-1-yl)-(3-phenyl-5-methyl-pyrazol-1-yl)]borate} with cadmium(Ⅱ) and cobalt(Ⅱ) acetate respectively, and structurally characterized. The title complexes feature distorted trigonal dipyramidal geometries with a S₄H donor set defined by the sulphur and hydrogen atoms of two tripodal sulfur-rich ligands. CCDC: 235514, 1; 244021, 2.     

多孔有机聚合物负载钌催化的β-酮酸酯的不对称氢化（英文）

合成了一种手性1,1'-联萘-2,2'-二苯膦(BINAP)功能化的多孔有机聚合物,用碳固体核磁谱(~(13)C CP/MAS NMR)、磷固体核磁谱(~(31)P CP/MAS NMR)、傅里叶变换红外光谱(FT-IR)、粉末X射线衍射(PXRD)、扫描电子显微镜(SEM)、透射电子显微镜(TEM)、氮气吸附和热重分析(TG)对材料进行表征,这个材料具有无定型的微孔结构.与Ru(II)络合后,复合材料Ru/POP-BINAP可非均相催化β-酮酸酯的不对称氢化,并表现出优良的催化活性、对映选择性和循环性.     

N4-calix[6]arene及其铜锌配合物的合成与电喷雾质谱表征

酶的高选择性和高效催化作用使生命体能在温和条件下进行化学反应.研究发现[1]酶的活性部位具有特定的结构,可以通过体积识别、氢键、配位键等非共价相互作用对底物进行选择性识别.     

新型一维麻花状超分子配合物的合成与结构

具有特殊结构及性能的超分子化合物由于其结构上的新颖性及潜在的应用价值而成为人们关注的热点 .以一个苯环为间隔基两端含两个吡啶基团的配体 L1与 Pd( ) ,Pt( )形成 2 -索烃 [1 ] ,与Cd( NO3) 2 则形成具有一维平面结构的聚合物 [2 ] .以联苯为间隔基的配体 L2在 4 ,4′-二联吡啶共同作用下与 Pd( )形成 2 -索烃 [3] .同样以一个苯环为间隔基两端含两个咪唑基团的配体 L3与 Zn( NO3) 2 ,Ag NO3反应得到新型多聚轮烷配合物 [4,5 ] .研究结果表明 ,配体或配位金属离子等的微小差别即导致形成结构不同的超分子化合物 .但这些超分子…     

Syntheses,Crystal Structures and Fluorescence Properties of Four Coordination Polymers Based on Enantiomeric 2-(4-Carboxyphenyl)-4,5-dihydrothiazole-4-carboxylic Acid Ligands

A pair of enatiomerically pure ligands,(R-)/(S-)2-(4-carboxyphenyl)-4,5-dihydrothiazole-4-carboxylic acid(H2L^R & H2L^S), have been synthesized by the reactions of 4-cyanobenzoic acid with L-and D-cysteine, respectively. Four coordination polymers have been prepared from the ligands and structurally determined by single-crystal X-ray diffraction analysis. Complexes 1 R and 1 S([NiL(Py)(H2 O)]×H2 O, for 1 R, L =(L^R)^2-;for 1 S, L =(L^S)^2-) exhibit chiral helical one-dimensional chains, and complexes 2 R and 2 S({[ZnL2(H2 O)3]×CH3 CN}n, for 2 R L =(L^R)^2-, for 2 S L =(LS)^2-) are two-dimensional sheets. Luminescent and chir-optical properties have been investigated and compared with the free ligands. The complexes have blue-shift in luminescence spectrum compared with the free ligands.     

水相中微孔有机聚合物负载钯催化的碳-碳偶联反应（英文）

合成了一种2,2'-联吡啶功能化的微孔有机聚合MOP-bipy,与Pd(CH3CN)2Cl2络合后得到一种复合材料Pd/MOP-bipy.用碳固体核磁(13C CP/MAS NMR)、傅里叶变换红外光谱(FT-IR)、粉末X射线衍射(PXRD)、扫描电子显微镜(SEM)、透射电子显微镜(TEM)、氮气吸附(nitrogen adsorption)和热重分析(TG)对材料进行表征.用电感耦合高频等离子光谱(ICP)和X射线光电子能谱(XPS)确定了Pd/MOP-bipy材料中Pd的含量和价态.该复合材料在水相催化Suzuki-Miyaura反应和甲醇与水的混合溶剂中催化Sonogashira偶联反应中表现出卓越的催化活性.Pd/MOP-bipy催化剂表现出至少五次循环的重复利用性.     

Cu(Ⅰ) and Cu (Ⅱ) helical complexes formed with oligobipyridine ligand

A new asymmetric oligobipyridine ligand, 1-(5'-methyl-2, 2'-bipyridin-5-yl)-2-(6'-methyl-2, 2'-bipyridin-6-yl)ethane (L), in which the bipyridine units are bridged by CH_2CH_2 at 5, 6'-position has been synthesized. The ligand L reacts with Cu(Ⅰ) and Cu(Ⅱ) ions giving double-stranded helical complexes [Cu_2~ⅠL_2] (ClO_4)_2·Et_2O (1) and [Cu_2~ⅡL_2 (OH) (H_2O)][ClO_4]_3(2), respectively. Complexes 1 and 2 were characterized by X-ray diffraction analyses, ES-MS, ESR and cyclic voltammetry, etc. Differing from the oligobipyridine ligands bridged by CH_2CH_2 at 6,6'-or 5,5'-position, the ligand L not only forms a double-stranded helicate with Cu(Ⅰ) ion, but also gives a double-stranded helicate with Cu(Ⅱ) ion. The results show that the linkage mode of the spacer group to the bipyridine units exerts a great impact on the formation of helix.     

基于杯芳烃的分子容器的合成及其对有机铵的可逆识别

将三(吡啶基甲基)胺(TPA)引入杯芳烃的下缘, 合成了一种新的具有杯状结构的杯芳烃衍生物, 研究了其对有机铵的分子识别行为.