Synthesis, Crystal Structure and Thermal Stability of Homopolytungstate Supporting Nickel(Ⅱ) Coordination Fragments

The organo-inorganic hybrid compound [ Ni(phen)3 ] [ ( H2W12O40 ) { Ni(phen)2H2O } { Ni(trien) } ]·2H2O was synthesized from Na2WO4·2H2O, NiSO4·6H2O, CH3COOK,triethylenetetramine and 1,10-phenanthroline in water by the hydrothernal reaction, and characterized by IR, X-ray single crystal diffraction, and TG-DTA analysis.This compound crystallized in the monoclinic system, space group P2 ( 1 )/n, with lattice constants: a = 1. 80998 (6) nm, b =2.36504(8) nm, c=2.29199(7) nm, β=110.2220(10)°, V=9.2065(5) nm, Z=4. Final R indices R1 =0.0532, wR2 =0.1295. The compound is decomposed at 593 ℃.     

Synthesis,Crystal Structure and Properties of a Novel Nickel Citrate Ni（H_2cit）（phen）（H_2O）·3H_2O（H_4cit = Citrate Acid,phen=1,10-Phenanthroline）

A new nickel citrate compound Ni(H2cit)(phen)(H2O).3H2O(H4cit = citrate acid,phen = 1,10-phenanthroline) has been synthesized and characterized by single-crystal X-ray diffraction.It crystallizes in the trigonal system,space group P31 with a = 13.8319(13),c = 10.425(2),V = 1727.3(4)3,Dc = 1.445 g/cm3,Mr = 501.09,F(000) = 780,μ = 0.901 mm-1,Z = 3,R = 0.0760 and wR = 0.1730 for 3859 observed reflections(I > 2σ(I)).In this compound,Ni2+ cation is chelated by a phen molecule,one H2cit2-anion and one H2O molecule.The citric acid coordinates to the Ni2+ center through three functional groups:α-hydroxyl,α-carboxylate and β-carboxylate while another α-carboxylate forms hydrogen bond with surrounding H2O molecule.And the citric acid is doubly protonated.The temperature-dependent magnetic susceptibility data revealed that the compound is a paramagnetic material.     

Synthesis, Characterization, and Properties of Supported Tungstozincate Bridged by Co(Ⅱ) Complex Fragment

[CoII(phen)3]2[{(ZnW12O40)CoII(phen)2(H2O)}2CoII(trien)2(NaH2O)2]·3H2O was synthesized via hydrothermal technique and characterized with elemental analyses, IR spectroscopy, TGA-DTA, and variable temperature magnetic susceptibility. The compound crystallized in the monoclinic system with the space group P21/n, a=1.8210 nm, b=2.3592 nm, c=2.2932 nm, β=110.31o, V=9.239 nm3, Z=2, R1=0.0827. The compound consists of two coordination cations, three lattice water molecules, and a macroanion [{(ZnW12O40)Co(phen)2(...     

Layered manganese 4-phosphonoisophthalates （4-piH4） embedding Mn-O chains with metamagnetism in Mn3（4-piH）2（H2O）3·H2O

Two manganese phosphonates Mn3(4-piH)2(H2O)3·H2O (1) and Mn5(4-piH)2(4-piH2)2(phen)2(H2O)4 (2) (4-piH4 = 4-phosphonoisophthalic acid, phen = 1,10-phenanthroline) have been synthesized under hydrothermal conditions in the presence of organic co-ligand. Both compounds exhibit layer structures but with different topologies. In compound 1, a complicated "ladder-like" chain of {Mn3O3}O2 which contains three- and six-member rings made up of triangular shaped {Mn3O3} trimers is found. The chains are linked by the PO3C groups to form an inorganic layer. The phenyl and protonated carboxylate groups are pendent between the layers with extensive hydrogen bonds. In compound 2, tetramers of {Mn4O6} are connected by the {MnO6} octahedra through corner-sharing to form an infinite chain, which is further bridged by 4-piH3- ligands into a thick hybrid layer. Magnetic measurements reveal that antiferromagnetic interactions are dominant in both compounds. Metamag- netism is observed in compound 1 at low temperature, while no long range ordering is found in compound 2 down to 1.8 K.     

Crystal Structure and Properties of the Calix[4]arene Derivative Containing Ethyl 2-Diazo-3-(ethylamino)-3-oxopropanoate Moieties

The target compound(C58H74N6O10) has been structurally determined by singlecrystal X-ray diffraction. The crystal is in the monoclinic system, space group C2/c, with a = 22.08(3), b = 12.628(19), c = 21.73(3) , β = 106.78(3)°, C58H74N6O10, Mr = 1015.23, Dc = 1.16239 g/cm3, V = 5801(14)3, Z = 4, F(000) = 2176, μ(MoKa) = 0.080 mm-1, T = 293(2) K, 5107 independent reflections with 3125 observed ones(I 2σ(I)), R = 0.0768 and w R = 0.2305 with GOF = 1.025(R = 0.1129 and w R = 0.2674 for all data). The calixarene moiety maintains the symmetric cone conformation through intramolecular O–H···O and N–H···O hydrogen bonds. The thermal analysis showed that the decomposition mechanism of compound 3 is complex. Fluorescence spectra of 3 exhibited an emission band at 423 nm when excited with 360 nm radiation at room temperature in DMF.     

苯四甲酸桥连的镍配合物[Ni(btec)(H2O)4][Ni(imi)2(H2O)4]·2H2O的合成及结构

At room temperature, a coordination polymer [Ni(btec)(H2O)4][Ni(imi)2(H2O)4]·2H2O was synthesized by reaction of NiCl2·6H2O, 1,2,4,5-benzenetetracarboxylic dianhydridc and imidazole in a water/THF solution. The structure was determined by X-ray diffraction crystal structure analysis. It crystallizes in triclinic P1 space group with the crystal cell parameters of a=0.67542 (2) nm, b=1.000 14 (1) nm, c=1.09088 (3) nm, α=74.140(2)°, β= 74.388(1)°, y=73.239(2)°, and V=0.664 09(3) nm3, Z=1. The crystal structure shows that Ni1 atom is coordinated by four water and two imidazole molecules, while Ni2 is coordinated by four water molecules and two carboxyl oxygen atoms. The 1,2,4,5-benzenetetracarboxylate ions bridge Ni2 coordination centers to form one-dimensional chain structure. Moreover, the chains are further linked together by hydrogen bonds to form a two-dimensional network. CCDC: 295873.     

Synthesis,Characterization, and Properties of Supported Tungstozincate Bridged by Co（Ⅱ） Complex Fragment

[Co^11（phen）3]2[{（ZnW12O40）Co^11（phen）2（H2O）}2Co^11（trien）2（NaH2O）2]·3H2O was synthesized via hydrothermal technique and characterized with elemental analyses, IR spectroscopy, TGA-DTA, and variable temperature magnetic susceptibility. The compound crystallized in the monoclinic system with the space group P21/n, a=1.8210 nm, b=2.3592 nm, c=2.2932 nm, β=110.31°, V=9.239 nm^3, Z=2, R1=0.0827. The compound consists of two coordination cations, three lattice water molecules, and a macroanion [{（ZnW12O40）Co（phen）2（H2O）}2Co（C6H18N4）2·（NaH2O）2]^4- in which each supported Keggin anion [（ZnW12O40Co^11（phen）2（H2O）]^4- acts as a ligand to coordinate to central bridging Co^2＋ ion via a terminal oxygen atom. Hydrogen bonds are responsible for the construction of 3D architecture of the compound. The compound is paramagnetic with a weak antiferromagnetic interaction（0=-46.796 K）.     

Hydrothermal Synthesis and Structure Characterization of Open-framework Cobalt-tungsten Phosphate[H3NCH2CH2NH3]3[Co3W4P4O28]

A new three-dimensional open-framework cobalt(Ⅱ)-tungsten(Ⅵ) phosphate,[H3NCH2CH2NH3]3·[Co3W4P4O28](1) has been synthesized from the reaction of CoCl2·6H2O,WO3,H3PO4,ethylenediamine and H2O.The title compound was fully characterized by infrared spectroscopy,elemental analysis,magnetic properties,thermogravimetric analysis,XPS and single-crystal X-ray diffraction.The compound crystallized in a tetragonal space group I4(1)/a with a=1.7118(4) nm,c=1.0773(2) nm,V =3.1568(11) nm3,Z =4.     

Synthesis and Crystal Structure of trans(N)-(1,10-Phenanthroline)-bis (DL-Al aninato)-Cobalt( Ⅲ ) Chloridetrihydrate

The title compound was synthesized by the reaction of cis-[Co(phen)2Cl2]Cl·3H2O with DL-alanine at pH = 8, and isolated using a column chromatographic method. Its crystal structure was determined. The crystal structure belongs to mono-clinic system, space group P21/c, with a = 0. 9549(6) nm, b=2.3746(8) nm, c= 1.0782(4) nm, β=114.13(3)°? Z = 4, Dc= 1. 50 g/cm3. The final refinement converged to R = 0. 047 for 3246 independent observed reflections. In the octahedral coordination sphere formed by the cobalt atom and the coordinate atoms, N, O of DL-alan-inato ligands are in the configuration of trans-N ,N form.     

A Novel Hydrogen-bonded Three-dimensional Network Complex Containing Nickel

A novel complex, (H3O)2[Ni(2,6-pydc)2] · 2H2O was synthesized in an aqueous solution and characterized by means of single-crystal X-ray diffraction, elemental analyses and IR spectra. The X-ray structural analysis revealed that the novel compound forms three-dimensional(3D) networks by both π-π stacking and hydrogen-bonding interactions. The crystal data for the complex are a = 13. 853 (3) nm, b= 9. 6892 (19) nm,c=13.732(3) nm, α=90. 00°, β=115.52(3)°, γ=90.00°, Z=3, R1=0. 0786, wR2=0.1522.     

二氧化碳和丙烯直接合成甲基丙烯酸的NiPMo/TiO2催化剂的研究

用溶胶-凝胶法以磷钼酸(MPA)的镍盐溶液水解钛酸四丁酯制备了NiPMo/TiO2催化剂.使用ICP、 XRD、 TG-DTA、 IR、 TPD-MS和微反应技术研究了催化剂的化学组成、热稳定性、化学吸附性质和催化反应性能.杂多钼酸盐与TiO2通过O2-在TiO2表面发生了键合.在623 K下,杂多阴离子仍保持原有的Keggin结构.CO2在Lewis酸位Ni(Ⅱ)和Lewis碱位Ni-O-Mo的桥氧协同作用下生成CO2卧式吸附态Ni(Ⅱ)←O-(CO)←(O--Ni).丙烯有多种吸附态在催化剂上吸附.在563 K、 1 MPa和空速1500 h-1的反应条件下,丙烯的摩尔转化率为3.2%,产物MAA选择性为95%.     

α-Amino acid derived enaminones and their application in the synthesis of N-protected methyl 5-substituted-4-hydroxypyrrole-3-carboxylates and other heterocycles

A new and simple synthesis of novel N-protected methyl 5-substituted-4-hydroxypyrrole-3-carboxylates, which exist in equilibrium with their 4-oxo tautomers, has been developed in two steps starting from N-protected α-amino acids. The key intermediates are enaminones, which can also be isolated, characterized, and used for the construction of other functionalized heterocycles, before they spontaneously decompose to pyrrole products. 4-Hydroxypyrroles are prone to partial aerial oxidation but can be efficiently alkylated or reduced to stable polysubstituted pyrrolidine derivatives.     

Specific intramolecular aromatic CH insertion of diazosulfonamides

The chemoselectivity in the intramolecular CH insertion of various diazosulfonamides has been experimentally studied. The results reveal that the aliphatic 1,4-, 1,5-, or 1,6-C(sp³)?H insertions of diazosulfonamides are not accessible, while the aromatic 1,5-C(sp²)?H insertion can be realized specifically by adjusting the diazo-adjacent group. In addition, the general chemoselectivities in the intramolecular CH insertions of diazosulfonyl compounds are summarized. Generally, diazosulfones undergo both aromatic 1,5-C(sp²)?H and aliphatic 1,5- and 1,6-C(sp³)?H insertions, while diazosulfonates undergo aliphatic 1,5- and 1,6-C(sp³)?H insertions. However, diazosulfonamides only undergo aromatic 1,5-C(sp²)?H insertion.     

N-Heterocyclic carbene-palladacyclic complexes: synthesis,characterization and their applications in the C-N coupling and α-arylation of ketones using aryl chlorides

N-Heterocyclic carbene-palladacyclic complexes 3 were successfully achieved in a one-pot procedure under mild conditions. The structure of 3a was unambiguously confirmed by X-ray single crystal diffraction and it was an active catalyst in the Buchwald-Hartwig amination and α-arylation of ketones even at very low catalyst loadings (0.01?mol%).     

Iodine-mediated oxidative Pictet-Spengler reaction using terminal alkyne as the 2-oxoaldehyde surrogate for the synthesis of 1-aroyl-β-carbolines and fused-nitrogen heterocycles

An efficient iodine-mediated oxidative Pictet-Spengler reaction in dimethyl sulphoxide (DMSO) using terminal alkynes as the 2-oxoaldehyde surrogate for the synthesis of aryl (9H-pyrido[3,4-b]indol-1-yl)methanones is described. The scope of the protocol includes the total synthesis of Fascaplysin, Eudistomins Y₁ and Y₂. The methodology is extended for preparing pyrrolo[1,2-a]-quinoxaline and indolo[1,5-a]quinoxaline derivatives. The utility of 1-aroyl-β-carbolines was demonstrated by performing palladium-catalyzed β-carboline directed ortho-C(sp2)-H functionalization of the phenyl ring with thiomethyl (SMe) group using DMSO as source and for accessing 4-aryl-canthin-6-ones.     

Facile synthesis of bicyclic 1-arylpyrazol-5-ones

In this Letter, we described a facile method for constructing fused bicyclic 1-arylpyrazol-5-one ring system. We employed various methylene-containing carboxylic acids as the substrates and proved that the pyrazolone ring closure requires activated methylene group in intermediate II. Accordingly, a series of structurally diversified, fused bicyclic 1-arylpyrazol-5-ones was prepared in moderate to high yields using the requisite substrates.     

CoFe2O4自形成磁性液体场致结构化对磁化的影响

The Langevin paramagnetic theory can’t describe the relation between magnetization of ferrofluids and applied magnetic field. The structuralization of ferrofluids, which is considered the main influence factor of the magnetization, is regarded. The part of magnetization works is deposited when the structure is forming. This action influences the magnetization of ferrofluids directly or indirectly. On the base of the “compressing” model, the Langevin function that usually describes the magnetization of ferrofluid is modified, and a well-fitted curve is obtained. An equation of the relation between the equivalent volume fraction after being “compressed” and the intensity of magnetic field is discovered, which approximately describes the process of magnetization. The relation between the approximate initial susceptibility and the volume fraction can be obtained from modified formula.     

Highly regioselective Buchwald–Hartwig amination at C-2 of 2,4-dichloropyridine enabling a novel approach to 2,4-bisanilinopyridine (BAPyd) libraries

The highly regioselective Buchwald–Hartwig amination at C-2 of the cheap and readily accessible reagent, 2,4-dichloropyridine with a range of anilines and heterocyclic amines is described. This new methodology is robust and provides a facile access to 4-chloro-N-phenylpyridin-2-amines on 0.25 mol scale. These intermediates undergo a further Buchwald–Hartwig amination at higher temperature to enable rapid exploration of the chemical space at C-4 and to provide a library of 2,4-bisaminopyridines.     

Sulfur-directed metal-free and regiospecific methyl C(sp3)–H imidation of thioanisoles

Regiospecific and direct imidation of the methyl C(sp³)–H bond of thioanisoles is realized under mild and metal-free conditions with N-fluorobis(benzenesulfonyl)imide as an oxidant and nitrogen source. Proposed mechanism suggests that thionium ion intermediates and a Pummerer-type reaction are involved. The imidation has advantages such as high step-economy, excellent functionality tolerance, and regiospecificity, giving structurally diverse imidation products.