A Novel Hybrid Solid Constructed from Tetramolybdate and Copper Complexes with Mixed Ligands: [{(Cu·phen)2(tp)}{(Cu·phen·H2O)2(tp)}{Mo4O14}]

A novel copper molybdate with mixed ligands, [{(Cu·phen)2(tp)}{(Cu·phen·H2O)2(tp)}{Mo4O14}] (phen=1,10-phenanthroline, tp=terephthalate) 1, has been hydrothermally synthesized and structurally characterized. The crystal belongs to monoclinic system, space group P21/c with a=13.1711(7), b=19.6132(10), c=13.6910(7) (A), β=117.6870(10)°, V=3131.8(3)(A)3, Z=2, C64H44Cu4Mo4N8O24, Mr=1946.99, Dc=2.065 g/cm3, F(000)=1920, μ(MoKα) (A) 2.198 mm-1, R=0.0810 and wR=0.2012 for 4233 observed reflections (Ⅰ ＞ 2σ(Ⅰ)). The structural analysis indicates that the title compound contains a discrete tetramolybdate cluster decorated with copper complex fragments and tp ligands bridging the clusters into a wave-like layer. The hydrogen bonding between adjacent layers further extends the compound into a 3-D framework.     

钴(Ⅱ)、镍(Ⅱ)-二甲酚橙多元络合物的光谱特性研究

研究了Co(Ⅱ)、Ni(Ⅱ)-NH3-XO混配络合物和Co(Ⅱ)、Ni(Ⅱ)-NH3-XO-CTMAB多元络合物的形成条件及吸收光谱特性,结果表明,在pH 9.5的氨性缓冲溶液中,[NH3]/[XO]值在100~400范围内所形成的钴、镍多元络合物的最大吸收波长分别为530和590 nm,钴的多元络合物在0~2.0 mg.L-1、镍的多元络合物在0~2.6 mg.L-1范围内符合比耳定律,相对标准偏差分别为2.1%和1.9%。     

新型混合固定相的制备与性能评价

通过共聚交联方法将长链碳烯-苯乙烯包覆到锆胶表面上, 得到聚合物包覆固定相, 再对该填料进行磺化引入离子官能团到聚合物表面, 得到混合型固定相. 用扫描电镜和红外光谱对这些填料进行了表征, 考察了混合型固定相的毛细管电色谱性能, 并用该填料分离了苯甲酸和苯胺等化合物.     

Mixed ligand complexes of AEE hexafluoroacetylacetonates with diglyme: Synthesis,crystal structure and thermal behavior

The novel mixed ligand complexes [Ca(hfa)₂(diglyme)(H₂O)] (I), [Sr(hfa)₂(diglyme)(H₂O)] (II) and [Ba(hfa)₂(diglyme)₂] (III) (Hhfa = 1,1,1,5,5,5-hexafluoropentane-2,4-dione, diglyme = 2,5,8-trioxanonane) were synthesized by the reactions of the alkaline earth element (AEE) carbonates in n-hexane with a mixture of Hhfa and diglyme, and they were characterized by elemental analysis, ¹H and ¹³C NMR, and FTIR spectroscopy. The crystal structures of I–III, consisting of mononuclear isolated molecules, have been determined. The thermal behavior and composition of the vapor phase have been studied for I–III by thermal analysis at low pressure and mass spectrometry using a Knudsen cell. The stability of the mixed ligand complexes [M(hfa)₂(diglyme)_n] to the removal of diglyme molecules under heating decreases in the row I > II ≈ III, and only I evaporates as the mixed ligand complex after water removal.     

Synthesis and solid-state structural characterisation of Pt(II,IV) bromide complexes containing bidentate organothiomethylpyridine heteroleptic ligands

A convenient synthetic method for the preparation of organothiomethylpyridine ligands 2-(RSCH₂)C₅H₄N (R = Ph (L¹), Me (L²)), 2-MeS–6-Me-C₅H₃N (L³), and 2-MeS–4-Me-C₅H₃N (L⁴) via the initial lithiation of substituted 2-picolines followed by the nucleophilic reaction with a diorganyldisulfide is described. The complexes [PtBr₂L] (L = L¹–L⁴) have been prepared in good to high yields as yellow solids with low solubility in organic solvents. The solid state structures of the complexes have been determined, showing the spatial arrangement of the complexes to depend significantly upon varying substituents within the ligand. The complexes undergo oxidation by bromine to form the tetravalent complexes [PtBr₄(L)] (L = L¹–L⁴). The solid state structures of [PtBr₄(L²)] and [PtBr₄(L₄)] have been determined, and shown to be monomeric with the ligand chelating the platinum centre.     

混合钴源对Co-Pd/TiO2催化剂催化CH4-CO2两步梯阶转化法合成乙酸的性能影响

以混合钴源为前驱体, 采用等体积浸渍法制备了Co-Pd/TiO2催化剂, 考察了其对CH4和CO2梯阶转化直接合成乙酸的催化性能, 采用XRD, XPS, NH3-TPD和BET对催化剂进行了表征. 结果表明, 催化剂具有适宜的表面酸性、 高比表面积和孔结构, 有利于提高催化剂的活性. 在m(CoCl2)∶m=2∶5, m(Co)∶m(Pd)=2∶1, 常压, 150 ℃条件下, 乙酸的生成速率达到6.13 mg·g-1Cat·h-1, 选择性达到 81.6%, 分别比以单一Co源制备的催化剂提高了134%和16%.     

2,2′-Bipyridyl-acetylphenolato mixed ligand copper(II) complexes: syntheses,characterizations and catalytic activity in styrene epoxidation

Two copper(II) complexes, [Cu(bipy)(5-Br-2-hap)(ClO₄)]₂ (1) and [Cu(bipy)(2-hap)(ClO₄)] (2) (where bipy?=?2,2′-bipyridine, 5-Br-2-hap?=?5-bromo-2-hydroxyacetophenone, 2-hap?=?2-hydroxyacetophenone), were synthesized and characterized. The crystal structure of 1 was determined by single crystal X-ray diffraction while 2 was reported earlier. Structural characterization reveals that the presence of bromine in 5-Br-2-hap plays a structure-determining role in dimeric 1 in comparison with the mononuclear 2 where 2-hap was used. Studies of the catalytic potential toward styrene epoxidation in homogeneous system using H₂O₂ as oxidant reveal that 1 is more efficient than 2 with respect to epoxide selectivity.     

新型笼状同多钒酸盐[Ni(1,10′-phen)3]2·[V2ⅣV8ⅤO26]的水热合成和晶体结构

尽管多金属氧酸盐(POMs)的研究已有180多年的历史, 但大量的POMs结构在最近几十年才被陆续解析出来[1～4].     

含混合价态钒的晶体[N(CH3)4]4[H5PMo5V9O42]·3.5H2O的合成与结构

含有钒和钼的化合物在催化、抗病毒药物、功能材料等领域具有广阔的应用前景 [1～ 4 ] .近年来 ,钒取代的杂多化合物或金属 -氧簇的合成与表征已引起人们的广泛关注 ,许多新的化合物已被合成 ,如含五价钒的化合物 K7[Mo8V5O4 0 ]· 8H2 O和 Na3[VMo12 O4 0 ]· 1 9H2 O[5,6 ] ,含有混合价态钒的簇阴离子[( V V Mo10 ) VO4 0 ]6 - 和 [Mo8V V4 O4 0 ]8- 的化合物 [7,8] ,含双帽 Keggin 结构的簇阴离子[PMo6 VMo6 O4 0 ( V O) 2 ]5- 和 [PMo8V 4 V 2 O4 2 ]5- 的化合物 [9,10 ] 等 ,但所报道的含混合价态钒的 V- Mo化合物中含…     

喷气燃料中悬浮物有机成分的气相色谱/质谱分析

本文研究了喷气燃料中悬浮物有机成分的分离和定性分析。先通过孔径0.025μm的微孔滤膜过滤分离出喷气燃料中的悬浮物,依次用正己烷和二氯甲烷提取悬浮物中的有机成分,再利用气相色谱/质谱联用技术对悬浮物的正己烷相溶液和二氯甲烷相溶液进行定性分析,共检测出了2,6-二叔丁基对甲酚、1,2-二氧芑-3-乙酸,6-十六烷基-3,6-二氢-6-甲氧基-甲基酯、5-甲基-5H-苯并[23-c]咔唑等47种成分,为研究悬浮物的形成机理提供了实验依据。