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51.
LI Yana b WU A-Qinga b ZHENG Fa-Kuna② GUO Guo-Conga② LU Can-Zhonga HUANG Jin-Shuna a 《结构化学》2005,(11)
1 INTRODUCTION Exploration on the syntheses and properties of car- boxylate complexes, especially aromatic carboxylate complexes, has always been a fascinating and chal- lenging research field for decades either in coor- dination chemistry or in functional materials[1, 2]. Cy- anobenzoic acid (Hcba) possessing two functional coordination groups should display structural diver- sities on the formation of complexes[3~15]. In particu- lar, the copper(II) carboxylate complexes bearing spe- … 相似文献
52.
Vojinović K McLachlan LJ Hinchley SL Rankin DW Mitzel NW 《Chemistry (Weinheim an der Bergstrasse, Germany)》2004,10(12):3033-3042
The simple silylhydrazines F(3)SiN(Me)NMe(2) (1), F(2)Si(N(Me)NMe(2))(2) (2), and F(3)SiN(SiMe(3))NMe(2) (3) have been prepared by reaction of SiF(4) with LiN(Me)NMe(2) and LiN(SiMe(3))NMe(2), while F(3)SiN(SnMe(3))NMe(2) (4) was prepared from SiF(4) and (Me(3)Sn)(2)NNMe(2) (5). The compounds were characterized by gas-phase IR and multinuclear NMR spectroscopy ((1)H, (13)C, (14/15)N, (19)F, (29)Si, (119)Sn), as well as by mass spectrometry. The crystal structures of compounds 1-5 were determined by X-ray crystallography. The structures of free molecules 1 and 3 were determined by gas-phase electron diffraction. The structures of 1, 2, and 4 were also determined by ab initio calculations at the MP2/6-311+G** level of theory. These structural studies constitute the first experimental proof for the presence of strong Si.N beta-donor-acceptor bonds between the SiF(3) and geminal NMe(2) groups in silylhydrazines. The strength of these non-classical Si.N interactions is strongly dependent on the nature of the substituent at the alpha-nitrogen atom of the SiNN unit, and has the order 3>4>1. The valence angles at these extremely deformed alpha-nitrogen atoms, and the Si.N distances are (crystal/gas): 1 104.2(1)/106.5(4) degrees, 2.438(1)/2.510(6) A; 3 83.6(1)/84.9(4) degrees, 2.102(1)/2.135(9) A; 4 89.6(1) degrees, 2.204(2) A. 相似文献
53.
《Chemphyschem》2003,4(6):588-594
The reorientational dynamics of the ionic liquid 1butyl‐3‐methylimidazolium hexafluorophosphate ([BMIM]PF6) were studied over a wide range of temperatures by measurement of 13C spin–lattice relaxation rates and NOE factors. The reorientational dynamics were evaluated by performing fits to the experimental relaxation data. Thus, the overall reorientational motion was described by a Cole–Davidson spectral density with a Vogel–Fulcher–Tammann temperature dependence of the correlation times. The reorientational motion of the butyl chain was modelled by a combination of the latter model for the overall motion with a Bloembergen–Purcell–Pound spectral density and an Arrhenius temperature dependence for the internal motion. Except for C2 in the aromatic ring, an additional reduction of the spectral density by the Lipari–Szabo model had to be employed. This reduction is a consequence of fast molecular motions before the rotational diffusion process becomes effective. The C2 atom did not exhibit this reduction, because the librational motion of the corresponding C2? H vector is severely hindered due to hydrogen bonding with the hexafluorophosphate anion. The observed dynamic features of the [BMIM]+ cation confirm quantum‐chemical structures obtained in a former study. 相似文献
54.
一个新的噻二唑衍生物H2ADTZ与锰的二维聚合物的合成与晶体结构(英) 总被引:2,自引:0,他引:2
A new 1,3,4 thiadiazole-derivative ligand 2,5-(s-acetic acid) dimercapto-1,3,4 thiadiazole (H2ADTZ) and its one-dimensional manganese polymer Mn(ADTZ)·4H2O had been synthesized and structurally characterized by X-ray single crystal diffraction in this paper. The Mn(Ⅱ) ion is coordinated with a distorted octahedron by two oxygen atoms from neighboring two deprotonated ligands ADTZ2- and other four oxygen atoms from four coordinated water molecules. The structural feature of the title compound is the formation of one-dimensional manganese chains polymer through the bridging of dioxygen O-O units. In the solid state structure of the complex, one-dimensional manganese chains are joined together by the weak intermolecular hydrogen bonds and vander Waals interactions forming a two-dimensional supramolecular compound. Furthermore, the UV spectra and electro-chemical properties of the title compound were also investigated. CCDC: 260532. 相似文献
55.
CHEN Wen-Tong GUO Guo-Cong ZENG Xi-Rui LI Xin-Fa FANG Xiao-Niu KUANG Han-Mao LIU Dong-Sheng LIU Li-Min 《结构化学》2007,26(10)
The title compound (4,4'-H2bipy)[CdBr4]·H2O 1 has been synthesized via hydrothermal reaction and characterized by X-ray diffraction. The crystal belongs to monoelinic,space group P21/c with a=8.260(3), b=23.926(7), c=9.774(2) (A), β=106.777(9)°,C10H12Br4CdN2O, Mr=608.26, V=1849.4(9)(A)3, Z=4, Dc=2.185 g/cm3, S=1.005, μ(MoKα)=9.814 mm-1, F(000)=1128, R=0.0646 and wR=0.0989. The crystal structure analysis of 1reveals that the title compound features an isolated structure, based on discrete 4,4'-H2bipy moieties and lattice water molecules which are linked by hydrogen bonds together with tetrahedral cadmium atoms terminally coordinated by four bromine atoms. 相似文献
56.
Furusho Y Oku T Hasegawa T Tsuboi A Kihara N Takata T 《Chemistry (Weinheim an der Bergstrasse, Germany)》2003,9(12):2895-2903
A dynamic covalent approach to disulfide-containing [2]- and [3]rotaxanes is described. Symmetrical dumbbell-shaped compounds with two secondary ammonium centers and a central located disulfide bond were synthesized as components of rotaxanes. The rotaxanes were synthesized from the dumbbell-shaped compounds and dibenzo-[24]crown-8 (DB24C8) with catalysis by benzenethiol. The yields of isolated rotaxanes reached about 90 % under optimized conditions. A kinetic study on the reaction forming [2]rotaxane 2 a and [3]rotaxane 3 a suggested a plausible reaction mechanism comprising several steps, including 1) initiation, 2) [2]rotaxane formation, and 3) [3]rotaxane formation. The whole reaction was found to be reversible in the presence of thiols, and thermodynamic control over product distribution was thus possible by varying the temperature, solvent, initial ratio of substrates, and concentration. The steric bulk of the end-capping groups had almost no influence on rotaxane yields, but the structure of the thiol was crucial for reaction rates. Amines and phosphines were also effective as catalysts. The structural characterization of the rotaxanes included an X-ray crystallographic study on [3]rotaxane 3 a. 相似文献
57.
Constantinos M. Paleos Dimitris Tsiourvas 《Angewandte Chemie (International ed. in English)》1995,34(16):1696-1711
The role of hydrogen bonding in the formation or stabilization of liquid crystalline phases has only recently been appreciated. Following the first, wellestablished examples of liquid crystal formation from the dimerization of aromatic carboxylic acids, through hydrogen bonding, several classes of compounds have recently been synthesized, the liquid crystalline behavior of which is also dependent on intermolecular hydrogen bonds between similar or dissimilar molecules. In this review the main classes of compounds exhibiting liquid crystallinity due to hydrogen bonding are presented to show the diversity of organic compounds that can be used as building elements in liquid crystals. The molecules are either of the rigid-rod anisotropic or amphiphilic types such as molecules appropriately functionalized with pyridyl and carboxyl groups, whose interaction leads to the formation of liquid crystals; amphiphilic carbohydrates and amphiphilic and bolaamphiphilic compounds with multiple hydroxyl groups whose dimerization or association is indispensable for the formation of liquid crystals; and certain amphiphilic carboxylic acids with monomeric or polymeric mesogens and amphiphilic-type compounds bearing different moieties, whose interaction may lead to the formation of mesomorphic compounds. Associated with the macroscopic display of liquid crystalline phases is the supramolecular structure, and therefore rather extended discussion of these structures are included in this review. 相似文献
58.
Erik Rakovský Ľudmila Žúrková Jaromír Marek 《Monatshefte für Chemie / Chemical Monthly》2002,133(3):277-283
Summary. Anhydrous 1,6-hexanediammonium dihydrogendecavanadate ((HdaH2)2H2V10O28, 1) was prepared by reaction of V2O5 with 1,6-hexanediamine in aqueous solution. The crystal structure of 1 was determined, and the proton positions in the H2V10O28
4− anion were calculated by the bond length/bond number method. The protons are bound to the centrosymmetrically oriented μ–OV3 groups of the decavanadate anion. Based on the analysis of IR spectra of 1 prepared from H2O and D2O, the absorption band at 871 cm−1 can be attributed to δ(V–Ob–H) vibrations.
Received August 3, 2001. Accepted (revised) October 8, 2001 相似文献
59.
New organohalogermanes RGe(OCH2CH2NMe2)2X (R = Ph, X = I (5); R = Me, X = Cl (6) or I (7)) with an intramolecular N→Ge coordination bond were synthesized. According
to the 1H and 13C NMR spectroscopic data, iodides 5 and 7 exist in solution as ionic compounds with the pentacoordinated germanium atom. In
solution of compound 4 (R = Ph, X = Cl), there is an equilibrium between the ionic and covalent forms. The equilibrium shifts
toward the ionic form with increasing solvent polarity or temperature. In solution, chloride 6 is a covalent compound. The
structures and relative stabilities of different isomers of compounds 4–7 were studied by quantum chemical calculations at
the density functional level of theory.
Published in Russian in Izvestiya Akademii Nauk. Seriya Khimicheskaya, No. 5, pp. 892–900, May, 2007. 相似文献
60.
V. G. Avakyan L. E. Gusel’nikov S. L. Gusel’nikov V. F. Sidorkin 《Russian Chemical Bulletin》2005,54(9):2013-2022
The effect of the nature of substituents at sp2-hybridized silicon atom in the R2Si=CH2 (R = SiH3, H, Me, OH, Cl, F) molecules on the structure and energy characteristics of complexes of these molecules with ammonia, trimethylamine,
and tetrahydrofuran was studied by the ab initio (MP4/6-311G(d)//MP2/6-31G(d)+ZPE) method. As the electronegativity, χ, of the substituent R increases, the coordination bond
energies, D(Si← N(O)), increase from 4.7 to 25.9 kcal mol−1 for the complexes of R2Si=CH2 with NH3, from 10.6 to 37.1 kcal mol−1 for the complexes with Me3N, and from 5.0 to 22.2 kcal mol−1 for the complexes with THF. The n-donor ability changes as follows: THF ≤ NH3 < Me3N. The calculated barrier to hindered internal rotation about the silicon—carbon double bond was used as a measure of the
Si=C π-bond energy. As χ increases, the rotational barriers decrease from 18.9 to 5.2 kcal mol−1 for the complexes with NH3 and from 16.9 to 5.7 kcal mol−1 for the complexes with Me3N. The lowering of rotational barriers occurs in parallel to the decrease in D
π(Si=C) we have established earlier for free silenes. On the average, the D
π(Si=C) energy decreases by ∼25 kcal mol−1 for NH3· R2Si=CH2 and Me3N·R2Si=CH2. The D(Si←N) values for the R2Si=CH2· 2Me3N complexes are 11.4 (R = H) and 24.3 kcal mol−1 (R = F). sp2-Hybridized silicon atom can form transannular coordination bonds in 1,1-bis[N-(dimethylamino)acetimidato]silene (6). The open form (I) of molecule 6 is 35.1 and 43.5 kcal mol−1 less stable than the cyclic (II, one transannular Si←N bond) and bicyclic (III, two transannular Si←N bonds) forms of this molecule, respectively. The D(Si←N) energy for structure III was estimated at 21.8 kcal mol−1.
Dedicated to Academician N. S. Zefirov on the occasion of his 70th birthday.
Published in Russian in Izvestiya Akademii Nauk. Seriya Khimicheskaya, No. 9, pp. 1952–1961, September, 2005. 相似文献