Solvothermal Synthesis and Characterization of （ NH3 CH2 CH2 NH3） HgSnS4 with a Column Structure

IntroductionSulfide-based open-framework materials are in-triguing compounds.They possess very diverse and in-teresting structures,and exhibit potential applicationsas a newgeneration of molecular sieves with the proper-ties of semiconductor materials[1].…     

Synthesis and Characterization of （CH3CH2CH2CH2NH3）2SnBr6

1 INTRODUCTION Recently, the researches on inorganic-organic hy-brid compounds represent an advanced field in mate-rial science[1]. At the molecular level, the combina-tion of two extremely different components providesan avenue to design new hybrid materials as well asthe ability to modulate properties of one or more ofthe components[2～6]. Some attractive properties, suchas efficient luminescence[2～4], ideal thermal and me-chanical stability, interesting magnetic[5], non-linearoptical[…     

Synthesis and Characterization of [NH3（CH2）2NH2（CH2）2NH3]BiCl6

1 INTRODUCTION During the past decade, a series of organic-inor- ganic hybrid compounds based on metal halide units have been prepared and studied[1]. The combination of organic and inorganic components at the mole- cular level affords us the opportunity to design new hybrid materials and modulate the properties of components[2]. As a result, some interesting proper- ties, such as non-linear optical[3], interesting magne- tic[4], efficient luminescence[2], ideal thermal and mechanical sta…     

Syntheses and Characterizations of （CH3CH2CH2CH2NH3）6（BiI6）（I）2I3 and （NH3CH2CH2NH3）2Bi2I10

The title compounds have been respectively synthesized by solution process and solvothermal reaction, and their crystal structures were determined by X-ray diffraction method. For （CH3CH2CH2CH2NH3）6（BiI6）（I）2I3 1, it crystallizes in tficlinic, space group P1^- with Mr = 2049.76, a = 8.5719（1）, b = 11.7461（3）, c = 15.700（1）A, V = 1451.4（1）A^3, Z = 1, Dc = 2.345 g/cm^3, F（000） = 924, μ（MoKα） = 8.907 mm^-1, T = 293（2） K, the final R = 0.0655 and wR = 0.0804 for 2399 observed reflections with I 〉 2σ（I）. For （NH3CH2CH2NH3）2Bi2I10 2, it crystallizes in monoclinic, space group P21/n with Mr= 1811.20, a = 8.434（4）, b = 13.862（6）, c = 13.362（6）A, V = 1499.9（12）A^3, Z = 2, Dc = 4.010 g/cm^3, F（000） = 1536,μ（MoKα） = 22.007 mm^-1, T = 293（2） K, the final R = 0.0584 and wR = 0.1451 for 1798 observed reflections with I 〉 2σ（I）. The structures of 1 and 2 contain halobismuthate monomer and dimers, respectively. It is noteworthy that the dimers and their organic counters in 2 connect each other by N…I hydrogen bonds to form a layered structure, and the electrostatic interactions and crystal packing forces between layers give rise to the packing of the crystal. The optical absorption spectra of 1 and 2 reveal the appearance of sharp optical gaps of 2.13 and 2.01 eV, respectively.     

Synthesis and characterization of glycol-modified vanadium(V) oxoisopropoxide and their oximato derivatives: sol–gel transformations of [VO(OPr i )3], [VO{OCH2CH2OCH2CH2O}{OPr i }] and [VO{OCH2CH2OCH2CH2O}{ON=C(CH3)(C4H3S-2)}] to vanadia

Reaction of [VO(OPr ⁱ )₃] (1) with [O(CH₂CH₂OH)₂] in 1:1 molar ratio in anhydrous benzene yield glycol-modified precursor, [VO{OCH₂CH₂OCH₂CH₂O}{OPr ⁱ }] (2). Further reactions of (2) with internally functionalized oximes in anhydrous benzene yield heteroleptic complexes of the type [VO{OCH₂CH₂OCH₂CH₂O}{ON=C(R)(Ar)}] (3–8) {where R=CH₃, Ar=C₄H₃O-2 (3), C₄H₃S-2 (4), C₅H₄N-2 (5); and when R=H, Ar=C₄H₃O-2 (6), C₄H₃S-2 (7), C₅H₄N-2 (8)}. All these derivatives have been characterized by elemental analyses, molecular weight measurements and spectroscopic techniques. The crysoscopic molecular weight measurement as well as FAB mass study suggests dimeric nature of (2). However, FAB mass spectrum of (4), and the crysoscopic molecular weight measurements of (3), (4), (5) and (6) indicate the monomeric behavior of the oximato derivatives (3–8). Hexa-coordination around vanadium(V) has been proposed for both monomeric and dimeric derivatives. Sol–gel transformations of (1), (2) or (4) to vanadia [(a), (b) or (c), respectively] have been carried out at low sintering temperature (600 °C). The XRD patterns of (a), (b) or (c) indicate formation of a single orthorhombic phase in all the three cases. The SEM images suggest grain like [for (a) and (b)] and rod like [for (c)] morphology of the crystallites. IR, Raman spectra as well as EDX analyses indicate formation of pure vanadia. Absorption spectra of the vanadia (b) and (c) suggest energy band gaps of 2.53 and 2.65 eV, respectively.     

配合物RuCl2（bdpx）（NH2CH2CH2NH2）的合成及其催化活性

合成了一种新的双膦-钌-二胺配合物——Rucl2（bdpx）（N心CH2CH2NH2）[bdpx=邻-二（二苯基膦）二甲苯]（1）,并研究了1催化苯乙酮（2）的加氢反应。在10．032mmol,n（2）：n（Me3COK）：n（1）=10000：120：1,氢气压力为3MPa的条件下,于70℃反应4h,2的转化率达100％。     

钒磷酸盐(NH3CH2CH2NH2)[VOPO4]的水热合成和结构表征

标题化合物是在反应物摩尔比为V2O5H3PO4H2NCH2CH2NH2H2O=0.5543.6265时,175℃水热反应5 d合成的.其结构特点是钒八面体[VO5N]共用角顶的氧形成"之"字型链,链间由[PO4]共角项连接成层;乙二胺分子的一个N直接与V配位,并伸向层间.相邻层间存在强氢键.晶体学数据单斜晶系,P21/c(No.14),a=0.92108(2)nm,b=0.72851(1)nm,c=0.98204(2)nm,β=101.269(7)°,V=0.6462(4)nm3,Z=4,Dc=2.303g·cm-3,R1=0.0417,wR2=0.0999.     

二维配位聚合物(NH3+CH2CH2NH3+)(NH2CH2CH2NH3+)2[(VO)4(PO4)4(H2O)2]·2H2O的水热合成及晶体结构

无机-有机杂化钒氧酸盐由于其结构的多样性以及在催化、医药、光、电、磁等材料领域中的应用前景而受到人们的广泛关注。近年来这一研究领域的重大进步是将有机氮配体或者过渡金属配合物直接连接到矾氧骨架上以获得各种新奇结构。合成出许多属于L/V/O、MXLY/V/O、L/P/V/O和MXLY     

含有NH2CH2CH2CH2NH2和o-C6H4(NH2)2配体的镍配合物的合成、结构和它们在乙烯聚合中的作用

两种镍的配合物[Ni(NH2CH2CH2CH2NH2)3]Cl2 (1)和[Ni(C6H4N2H4)2Cl2] (2)已经被合成并且通过红外和单晶X射线衍射分析对其进行了表征。在配合物1中,镍原子处于手性假八面体[NiN6]的几何构型中,它与三个1,3-丙二胺分子形成了三个六元环。在配合物2中,镍原子除了与两个o-苯二胺分子通过四个Ni-N键形成两个五元环外,它还与两个Cl原子配位形成了反式Ni-Cl2,这不同于以往报道过的镍的二胺配合物。这两个镍的配合物被MAO, MMAO或Et2AlCl活化后,对乙烯的二聚合或三聚合显示了很好的催化活性[对于配合物2,催化活性达到3.59×106 g mol-1 (Ni) h-1]。     

双膦配合物RuCl2(dppe)(NH2CH2CH2NH2)的合成及催化性能研究

合成了双膦配合物RuCl2(dppe)(NH2CH2CH2NH2)[dppe=1,2-二(二苯膦基)乙烷]。考察了此配合物对苯乙酮及其衍生物加氢反应的催化性能,并对各种反应参数变化对加氢反应的影响进行了详细的研究。结果表明,此配合物对苯乙酮的加氢反应具有良好的催化活性,在苯乙酮/(CH3)3COK/配合物的摩尔比为5000:40:1、氢气压力为3 MPa的条件下,于70℃反应5 h,苯乙酮的转化率可达到99.6%。     

Synthesis, Structure Characterization and Biological Activity of Layered Vanadium Oxides [ NH3 （ CH2 ）2 NH （ CH2 ）2 NH3 ] [ V6 O14 ]

Introduction Over the past decades, polyoxometalates(POMs)have been attracting extensive interestowing to the widerange of their topological properties and potential appli-cations in catalysis, photochemistry, electrochromism,and magnetism[1,2]. Meanwhile, owing to the potentialapplication of polyoxometalaes as anticancer and antivi-ral drugs, their complexes have attracted increasing in-terest of both inorganic chemists and biochemists[3]. Itis well known that polyoxometalates are excellent …     

A cobalt molybdenum phosphate with a tunnel: Hydrothermal synthesisand structure of (NH3CH2CH2NH3)4·(NH3CH2CH2NH2)·Na·[Co2Mo12O30(PO4)(HPO4)4(H2PO4)3]·5H2O

Transition Metal Chemistry -     

Vibrational circular dichroism of 2,6-di-sec-butyl-4-methylpyridine and 2,6-di-sec-butyl-4-methylpyridine-N-oxide: theoretical evidence on the existence of multiple –CH, –CH2, and –CH3⋯O intramolecular hydrogen bonds on the nitroxide oxygen

Enantiopure (±)-2,6-di-sec-butyl-4-methylpyridine and its oxidized form (±)-2,6-di-sec-butyl-4-methylpyridine-N-oxide were prepared and then separated by chiral HPLC. Their stereochemical structures and their conformational distribution in solution were investigated using vibrational circular dichroism (VCD) and infrared spectroscopy (IR) combined with density functional theory (DFT). The experimental spectra have been compared with theoretical data. This comparison indicated that (−)-2,6-di-sec-butyl-4-methylpyridine and its oxidized form (+)-2,6-di-sec-butyl-4-methylpyridine-N-oxide have an (S,S)-configuration and exist in several conformations. The good fit confirms the reliability of the conformational analysis. Our results indicated that going from the reduced form to the oxidized one strongly influences the type of conformers in solution. Moreover, DFT calculations showed that for all of the conformers of (S,S)-2,6-di-sec-butyl-4-methylpyridine-N-oxide, the formation of four centered intramolecular hydrogen bonds between the hydrogen of the –CH, –CH₂, and –CH₃ groups and the nitroxide oxygen is possible. Moreover the stability of the conformers of both compounds is influenced by the all-trans structure of the sec-butyl moieties.     

Effects of substituents and charge on the RCHO⋯X–Y {X = Cl,Br, I; Y = –CF3, –CF2H, –CFH2, –CN, –CCH, –CCCN; R = –OH, –OCH3, –NH2, –O−} halogen-bonded complexes

Structural Chemistry - Noncovalent interactions involving halogen bonding interactions, one of the emerging interactions due to its directionality, have been a subject of interest for various...     

Structure of [NH3(CH2)4NH3]2P4O12·2H2O

After a short survey of what is the present state of the cyclophosphates associated with the organic molecule NH₂(CH₂)₄NH₂, we report chemical preparation and crystal structure for a new example of such compounds. [NH₃(CH₂)₄NH₃]₂P₄O₁₂.2H₂O is monoclinic (S.G. : P2₁/n), with Z = 2 and the following unit-cell parameters : a = 7.6728(8) Å, b = 18.962(3) Å, c = 7.9789(9) Å β = 111.751(9)°. Bidimensional layer arrangement of P₄O₁₂ rings connected to the water molecules thanks to weak H-bonds run parallel to the ab plane. The organic groupements located between these inorganic planes perform the three-dimensional cohesion by NH····O hydrogen bonds.     

Solvothermal synthesis of two polymorphs of an indium germanate incorporating an organic amine ligand: β- and γ-In2Ge6O15(NH2CH2CH2NH2)2

Two new polymorphs, β- and γ-In(2)Ge(6)O(15)(NH(2)CH(2)CH(2)NH(2))(2), have been synthesized under solvothermal conditions using 2-methylpentamethylenediamine as a solvent and structurally characterized by single-crystal X-ray diffraction. Both structures contain single layers with the composition [Ge(6)O(15)] that are connected by In(2)O(6)N(4) octahedral dimers to form 3D frameworks. The germanate layers contain four-, six-, and eight-membered rings and six-membered rings in the β and γ polymorphs, respectively. Compounds with related structures are discussed for comparison.     

Relative permittivity increments for {xCH3OH + (1 − x)CH3OCH2(CH2OCH2)3CH2OCH3} fromT = 283.15 K toT = 323.15 K

Relative permittivities of { CH₃OH  +  CH₃OCH₂(CH₂OCH₂)₃CH₂OCH₃(2,5,8,11,14-pentaoxapentadecane, tegdme)} at temperatures from 283.15 K to 323.15 K and atmospheric pressure, were measured over the whole composition range. Experimental relative permittivities were fitted by a polynomial function in mole fraction. Values of relative permittivity were measured using a HP4284A precision LCR Meter together with the measuring cell HP16452A at 1 MHz. Relative permittivity increments were determined from experimental data and fitted to a variable-degree polynomial function. Different theoretical models were used to predict the permittivity of this mixture. The predictions are better when the volume change on mixing is considered.     

Mild Deprotection of tert‐Butyl Carbamates of NH‐Heteroarenes under Basic Conditions

Aqueous methanolic potassium carbonate under reflux has been demonstrated to be a highly effective deprotective agent for the tert‐butyl carbamates of indoles, indazoles, carbazole, thiazoloindole, and pyrrole. The method is a mild one and is particularly expeditious for NH‐heteroarenes bearing electron‐withdrawing groups.     

CH3OCF2CF2OCH3+Cl的反应机理及动力学性质

利用密度泛函理论直接动力学方法研究了反应CH₃OCF₂CF₂OCH₃+Cl的微观机理和动力学性质. 在BB1K/6-31+G(d,p)水平上获得了反应的势能面信息, 计算中考虑了反应物CH₃OCF₂CF₂OCH₃两个稳定构象(SC1和SC2)的氢提取通道和取代反应通道. 利用改进的正则变分过渡态理论结合小曲率隧道效应(ICVT/SCT)计算了各氢提取通道的速率常数, 进而根据Boltzmann配分函数得到总包反应速率常数(k_T)以及每个构象对总反应的贡献. 结果表明296 K温度下计算的k_T(ICVT/SCT)值与已有实验值符合得很好. 由于缺乏其他温度速率常数的实验数据, 我们预测了该反应在200-2000 K温度区间内反应速率常数的三参数表达式: k_T=0.40×10^-14T^1.05exp(-206.16/T).     

[ZnN(CH2CH2NH2)2(CH2CH2N=CHC6H4O)]·Pic的合成与晶体结构

在不加任何碱的条件下,三[2-(亚水杨基胺)乙基]胺与苦味酸锌[Zn(Pic)26H2O]在乙醇中反应,得到了较为少见的多胺单缩合西夫碱配体的配合物[ZnN(CH2CH2NH2)2(CH2CH2N=CH-C6H4O)]Pic。化学式为C19H23N7O8Zn,Mr=542.81,晶体属三斜晶系,空间群为P,晶胞参数为a=0.7494(3),b=1.1917(5),c=1.3142(6)nm,a=78.111(7),b=79.093(7),g=78.577(7),V=1.1121(8)nm3,Dc=1.621g/cm3,m(MoKa)=1.167mm-1,Z=2,F(000)=560,在1.602s(I)的可观测点为2433个,最终偏离因子R=0.0555,wR=0.1139。配合物中Zn(II)与配体的4个N原子和1个O原子配位形成变形的三角双锥结构,桥头N和O为锥顶,4个配位N中桥头N与金属离子的配位作用最弱。晶体通过p-p堆积和分子内、分子间的氢键作用形成二维层状超分子结构。