Pyrazole-3-carboxylic Acid Manganese Complex: Syntheses and Its highly Efficient Heterogeneous Catalysis for the Epoxidation of Alkenes

One inorganic-organic hybrid manganese complex Mn(Hpca)2(phen)·3 H_2O(1) based on pyrazole-3-carboxylic acid(H2 pca) and phenanthroline(phen) has been synthesized and fully characterized by single-crystal X-ray diffraction(SXRD), powder X-ray diffraction(PXRD), infrared spectroscopy(IR), thermal gravity analysis(TGA) and elemental analyses. Complex 1 crystallizes in the monoclinic system, space group P2_1/c with Z = 4, a = 10.3170(9), b = 13.1061(12), c = 17.6919(15) ?, V = 2272.1(3) ?~3, F(000) = 1052, D_c = 1.495 g/cm~3, μ = 0.635 mm~(-1), the final R = 0.0428 and wR = 0.0853. In the crystal structure, the mononuclear Mn~(2+) center was coordinated by two Hpca-and one phen ligands, and shows a distorted {MnO_2N_4} octahedral coordination geometry. In the supermolecular structure, the independent units are entrained within several hexanuclear chair-like water clusters by the O-H···O and N-H···O hydrogen bonding interactions and finally form the three-dimensional framework. Notably, as a robust heterogeneous catalyst, complex 1 exhibits excellent catalytic performance in the epoxidation of alkenes with peroxyacetic acid as the oxidant(Conv. up to 97.7%, Sele. up to 98.9%). Additionally, the catalyst can be reused without losing its activity after three runs catalytic cycle.     

吡唑-3-甲酸Cu(Ⅱ)/Mn(Ⅱ)配合物的合成、表征及常压下对二氧化碳催化转化

合成和表征了2个吡唑-3-甲酸过渡金属配合物[Cu₂（pca）₂（H₂O）₆]·2H₂O（1）,[Mn（Hpca）₂（phen）]·3H₂O（2）（H₂pca=吡唑-3-甲酸;phen=菲咯啉）。X射线单晶衍射分析结果表明,配合物1属于单斜晶系P2₁/n空间群,它是一个畸变八面体的双核铜配合物;配合物2是一个畸变八面体的单核锰配合物。配合物1和2分别通过分子间的O-H…O,N-H…O氢键形成了三维网状结构。配合物1在二氧化碳的环加成反应中显示出了良好的催化效率（转化率高达97.4%;选择性高达98.9%）。     

两个2,4-二羟基苯甲醛缩甘氨酸配合物的合成、结构及其对醇的选择性氧化催化

合成和表征了2个2,4-二羟基苯甲醛缩甘氨酸(H₃L)席夫碱配合物[Cu(Py)₂(HL)] (1)和[Zn(Py)₃(HL)]·2Py(Py=吡啶) (2),并通过X射线单晶衍射分析确定了其结构.配合物1通过分子间的O-H…O氢键形成了一维链状结构,配合物2通过分子间的O-H…O和C-H…O氢键形成了二维网状结构.重要的是,配合物1在醇的选择性氧化反应中显示出了良好的催化效率(转化率高达94.8%,选择性高达98.3%).     

Two Copper Complexes Based on Pyrazole-3-carboxylic Acid as Heterogeneous Catalysts for Highly Selective Oxidation of Alkylbenzenes

Two new copper complexes based on pyrazole-3-carboxylic acid(H_2pca)ligand,Cu(Hpca)_2(H_2O)_2·2H_2O(1)and Cu_2(pca)_2(H_2O)_4(2)have been synthesized and fully characterized by single-crystal X-ray diffraction(SXRD),infrared spectroscopy(IR),thermal gravity analysis(TGA),powder X-ray diffraction(PXRD)and elemental analyses.Complex 1 is mononuclear while complex 2 shows a dinuclear structure.Complex 1 crystallizes in the monoclinic system,space group P2_1/c with Z=2,a=6.5591(5),b=21.696(2),c=4.9486(2)?,V=680.94(9)?~3,F(000)=366,D_c=1.745 g/cm~3,μ=1.650 mm~(-1),the final R=0.0340 and w R=0.0792.Complex 2crystallizes in the monoclinic system,space group P2_1/n with Z=2,a=5.1935(4),b=9.6052(7),c=12.7347(9)?,V=634.44(8)?~3,F(000)=420,D_c=2.195 g/cm~3,μ=3.404 mm~(-1),the final R=0.0305 and w R=0.0653.The three-dimensional frameworks of two complexes are formed by the O-H···O and N-H···O hydrogen bonding interactions.Notably,two copper complexes are further used as catalysts in the oxidation of alkylbenzenes using t-butylhydroperoxide(TBHP)as the oxidant and they exhibit excellent catalytic performance(Conv.up to 98.9%,Sele.up to 98.7%).     

Synthesis,Crystal Structure and Fluorescence Properties of a 3D Framework Based on Hexanuclear Lanthanum 5-Nitroisophthalate Entities

The reaction of lanthanum(Ⅲ) nitrate and 5-nitroisophthalic acid in isopropanol/H2O under hydrothermal conditions leads to a 3D lanthanum-containing coordination polymer with the general chemical formula {[La6(Nip)9(H2O)4 ]·(H2O)4 }∞(1,Nip=5-nitroisophthalate).The single-crystal X-ray analyses show that this compound crystallizes in the orthorhombic system,space group Ima2 with a=9.7769(12),b=28.239(3),c=21.149(2),V=5839.1(11)3,Z=2,Mr=2859.61,Dc =1.626 g/cm 3,F(000)=2752.14040 reflections are collected,of which 5275 are unique (R int=0.0241).Final GOOF=1.083,R=0.0406 and wR=0.1182,R indices based on 5183 reflections with I>2σ(I)(refinement on F2),443 parameters,1 restraint.Lp and absorption corrections were applied,=2.242mm-1.Absolute structure parameter x=0.08(3).The crystal structure can be described as the butterfly-liked hexanuclear lanthanum entities {La6O6(CO2)8 } covalently linked to each other by nitroisophthalate ligands into an intricate three-dimensional structure.The fluorescence spectroscopy of compound 1 has been investigated.     

两个2,4-二羟基苯甲醛缩甘氨酸配合物的合成、结构及其对醇的选择性氧化催化

合成和表征了两个2,4-二羟基苯甲醛缩甘氨酸(H₃L)席夫碱配合物[Cu(Py)₂(HL)] (1)和[Zn(Py)₃(HL)]·2Py(Py=吡啶) (2),并通过X射线单晶衍射分析确定了其结构。配合物1通过分子间的O-H…O氢键形成了一维链状结构,配合物2通过分子间的O-H…O和C-H…O氢键形成了二维网状结构。重要的是,配合物1在醇的选择性氧化反应中显示出了良好的催化效率(转化率高达94.8%,选择性高达98.3%)。     

微波促进苄基溴化锌与肉桂醛的烯基化反应

在Me3SiCl和Pd（PPh3）2Cl2存在下,通过微波辐射带官能团的苄基溴化锌与肉桂醛反应高效地合成了含不同官能团的1,4-二苯基-1,3-丁二烯类化合物,收率65％-95％,其结构经1^H NMR,13^C NMR,IR和MS确证。     

吡唑-3-甲酸Cu(Ⅱ)/Mn(Ⅱ)配合物的合成、表征及常压下对二氧化碳催化转化

合成和表征了2个吡唑-3-甲酸过渡金属配合物[Cu₂（pca）₂（H₂O）₆]·2H₂O（1）,[Mn（Hpca）₂（phen）]·3H₂O（2）（H_2pca=吡唑-3-甲酸;phen=菲咯啉）。X射线单晶衍射分析结果表明,配合物1属于单斜晶系P2¹/_n空间群,它是一个畸变八面体的双核铜配合物;配合物2是一个畸变八面体的单核锰配合物。配合物1和2分别通过分子间的O-H…O,N-H…O氢键形成了三维网状结构。配合物1在二氧化碳的环加成反应中显示出了良好的催化效率（转化率高达97.4%;选择性高达98.9%）。     

不同构象表示法使用Cram规则的探讨

Cram经验规则在判断与手性中心相连羰基的亲核加成立体选择性方面具有重要应用,目前教材常采用Newman投影式结合Cram规则进行主要产物的预测,而当Cram规则使用于其他构象表示式如锯架式、伞形式及Fischer投影式时,需要先进行构象转换,这对学生的空间想象能力及抽象思维提出较高要求,导致在判断时容易出错,是有机化学学习的一个难点。通过对Cram规则的深入分析,介绍Cram规则如何直接应用于除Newman表示式外的常用构象表示式,以避免费时费力又容易出错的构象式转化。     

无溶剂条件下通过锌铜偶促进的Barbier反应合成羧酸酯

在锌酮偶的促进下,通过Barbier反应以醛、溴代烃和酸酐为原料,在无溶剂非催化条件下三组分"一锅法"反应合成了一系列高烯丙基酯、高炔丙基酯和β-乙酰氧基酯类化合物.对反应条件及历程也进行了探讨.该方法具有反应条件温和、操作简单、产率高、原料易得、反应迅速的特点.