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71.
Reaction of a Cyclic Bis(amino)germylene with Germaniumazides: Trapping-Reactions of Unstable Germa-Imines . The cyclic bis(amino)germylene 1 reacts with different germaniumazides of the type Me2Si(NtBu)2Ge(R)N3 (R = Me ( 2 ), tBu ( 3 ), N(SiMe3)2 ( 4 ), R = N3 ( 5 )). With the exception of 4 all azides lose dinitrogen when treated with 1 and the GeII center coordinates the α-nitrogen of the azide group. It seems to be reasonable to assume a transient germaimine (nitride) which is trapped by further reaction with the azide molecules 2 and 5 or by reaction with the solvent pyridine ( 3 ). In the case of 2 the germatetrazole [Me2Si(NtBu)2]GeN4[Ge(NtBu)2SiMe2]2 ( 6 ) is formed, the tetrazole nitrogens being exclusively substituted by germanium atoms (point symmetry of the molecule Cs(m)). When 1 is treated with 5 a tris(germa)amine [Me2Si(NtBu)2Ge(N3)]3N ( 8 ) is formed, which has an azide group attached to each Ge-atom. X-ray analysis reveals that the nine nitrogen atoms of the azide groups are coplanar with the trigonal planar Ge3N moiety (crystallographic symmetry: 3/m). The reaction of 1 with 3 is very surprising: the pyridine in the product Me2Si(NtBu)2Ge(C5H4N)? N(H)Ge(tBu)(NtBu)2SiMe2 ( 7 ) is bonded via an α-carbon atom while the remaining hydrogen has added to the nitride-nitrogen. 6 crystallizes in the monoclinic system space group C2/m, a = 24.306(9), b = 10.933(6), c = 19.420(9) Å, β = 91.81(2)° and Z = 4. 7 crystallizes in the hexagonal system space group P63/m with a = b = 16.73(1), c = 11.006(8) Å, γ = 120° and Z = 2, and 8 crystallizes in the monoclinic system space group P21/n, a = 11.341(6), b = 26.086(9), c = 13.244(7) Å, β = 98. I2(2)° mit Z = 4. 相似文献
72.
Pradip K. Bhowmik Robert W. Lenz 《Journal of polymer science. Part A, Polymer chemistry》1993,31(8):2115-2122
A series of fully aromatic thermotropic polyesters based on mono-, di-, and tetra-substituted biphenols was prepared by the melt polycondensation method and examined for their thermotropic behavior by a variety of experimental techniques. The homopolyesters obtained from substituted biphenols containing either one phenyl or two phenyl groups as substituent(s) and TA formed nematic melts, but the homopolymers of the substituted biphenols containing either four sec-butyl groups or two tert-butyl groups with TA had melting transitions, Tm, above 400°C. Thus, it was not possible to determine whether they formed nematic melts. On copolymerization with 30 mol % HBA most of the resulting copolyesters had much lower Tm values, compared to those of respective homopolyesters, and the copolymers of the biphenol monomer containing the tert-butyl groups formed a nematic melt at an observable temperature. However, the copolymer of the biphenol with sec-butyl groups still had a Tm above 400°C. © 1993 John Wiley & Sons, Inc. 相似文献
73.
Dr. Luca Fornasari Dr. Anna Olejniczak Dr. Federica Rossi Dr. Simone d'Agostino Prof. Michele R. Chierotti Prof. Roberto Gobetto Prof. Andrzej Katrusiak Prof. Dario Braga 《Chemistry (Weinheim an der Bergstrasse, Germany)》2020,26(22):5061-5069
The structures and solid-state dynamics of the supramolecular salts of the general formula [(12-crown-4)2 ⋅ DABCOH2](X)2 (where DABCO=1,4-diazabicyclo[2.2.2]octane, X=BF4, ClO4) have been investigated as a function of temperature (from 100 to 360 K) and pressure (up to 3.4 GPa), through the combination of variable-temperature and variable-pressure XRD techniques and variable-temperature solid-state NMR spectroscopy. The two salts are isomorphous and crystallize in the enantiomeric space groups P3221 and P3121. All building blocks composing the supramolecular complex display dynamic processes at ambient temperature and pressure. It has been demonstrated that the motion of the crown ethers is maintained on lowering the temperature (down to 100 K) or on increasing the pressure (up to 1.5 GPa) thanks to the correlation between neighboring molecules, which mesh and rotate in a concerted manner similar to spiral gears. Above 1.55 GPa, a collapse-type transition to a lower-symmetry ordered structure, not attainable at a temperature of 100 K, takes place, proving, thus, that the pressure acts as the means to couple and decouple the gears. The relationship between temperature and pressure effects on molecular motion in the solid state has also been discussed. 相似文献
74.
Heating ortho‐nitro‐anilides 1 – 3 and 2‐methyl‐N‐(3‐nitropyridin‐2‐yl)propanamide ( 5 ) with 4 equiv. of a phosphine led to the 2‐substituted benzimidazoles 6 – 8 and to the imidazo[4,5‐b]pyridine 10 , respectively, in yields between 45 and 85%. Heating 1 with (EtO)3P effected cyclisation and N‐ethylation, leading to the 1‐ethylbenzimidazole 6b . The slow cyclisation of the N‐pivaloylnitroaniline 2b allowed isolation of the intermediate phosphine imide 11 that slowly transformed into the 1H‐benzimidazole 7b . The structure of 11 was established by crystal‐structure analysis. While the N‐methylated ortho‐nitroacetanilide 3 cyclised to the 1,2‐dimethyl‐1H‐benzimidazole ( 8 ), the 2‐methylpropananilide 4 was transformed into 1‐methyl‐3‐(1‐methylethyl)‐2H‐benzimidazol‐2‐one ( 9 ). 相似文献
75.
The complexes [Te(etu)4][SiF6] (1), [Te(etu)4][SiF6] · H2O (2), [Te(trtu)4][SiF6] (3), [Te(etu)4][GeF6] · H2O (4), [Te(trtu)4][GeF6] (5) and [Te(etu)4][SnF6] (6) (etu = ethylenethiourea, trtu = trimethylenethiourea) have been prepared and their crystal structures determined by X-ray crystallographic methods. The crystals of 1, 3 and 5 are tetragonal; space groups P4cc (No. 103) with Z = 4 for 1, P4nc (No. 104) with Z = 2 for 3, and I4 (No. 79) with Z = 2 for 5. The crystals of 2, 4 and 6 are orthorhombic, space group Pccn (No. 56) with Z = 8 for 2 and 4 and Z = 4 for 6; those of 2 and 4 being isomorphous. The cations contain square planar or slightly distorted square planar TeS4 coordination groups. In 1, 3 and 5 the Te atoms are located on fourfold rotation axes; the cations have fourfold rotational symmetry and the four thiourea ligands extend to the same side of the TeS4 plane. These are the first examples of [TeL4]2+ conformers of this type. In 2 and 4 the Te atoms lie on general positions; the cations are distorted versions of those in 1, and also in these the four ligands extend to the same side of the TeS4 plane. In 6 the Te atoms are located on twofold rotation axes, the conformation of the cations corresponds to the point group C2 with two neighbouring ligands extending to one side of the coordination plane and the remaining two to the opposite side. In 1–5 each of the four ligands forms a N–HF bond to the same F atom in the counter ion. The crystals of 1–5 are red, and those of 6 are yellow. The red colour is attributed to interactions of Te and S lone electron pairs caused by ligand TeS4/TeSC tilt angles markedly different from 90°. 相似文献
76.
Thomas M. Klapötke Burkhard Krumm Dieter Naumann 《Journal of fluorine chemistry》2004,125(6):997-1005
The perfluoroaryl tellurolates C6F5TeLi (1) and 4-CF3C6F4TeLi (2) were prepared. These intermediates were identified by NMR spectroscopy and may form, depending on the reaction conditions, either the corresponding ditellanes C6F5TeTeC6F5 (3) and CF3C6F4TeTeC6F4CF3 (4) by subsequent oxidation, or in the case of 1, a telluranthrene (C6F4Te)2 (5) by reaction with itself. The halogenation products of 5, ( C6F4Te)2F4 (6), (C6F4Te)2Cl4 (7), (C6F4Te)2Br4 (8), as well as the azidation product (C6F4Te)2(N3)4 (9) were synthesized. Furthermore, in pursuit of our recent work on tellurium azides, the syntheses and properties of R2Te(N3)2 (R=CF3 (10), C6F2H3 (11)) and RTe(N3)3 (R=CF3 (12) and C6F5 (13)) are reported. The crystal structures of CF3C6F4TeTeC6F4CF3 (4), (C6F4Te)2Br4 (8), and (C6F2H3)2Te(N3)2 (11) were determined. 相似文献
77.
Intramolecular and liquid structure of 2,2,2-trifluoroethanol (TFE) have been investigated by x-ray diffraction at 25°C. The structural parameters for the skeleton of the molecules in the liquid phase are similar to those in the gas phase. The conformers of TFE molecules in the liquid phase are discussed. The O...O distance at about 284 pm and additional F...O one at about 302 pm were found to be characteristic for the first neighbor interactions. Various models (dimers and trimers) have been examined for analyzing the first neighbor structure. The liquid structure was explained in terms of small clusters consisting of two to three molecules rather than of a more extended polymeric network.Central Research Institute for Chemistry of the Hungarian Academy of Sciences, Budapest, P. O. Box 17, H-1525, Hungary. 相似文献
78.
《Journal of computational chemistry》2018,39(17):1038-1043
The Kernel energy method (KEM) is a quantum chemical calculation method that has been shown to provide accurate energies for large molecules. KEM performs calculations on subsets of a molecule (called kernels) and so the computational difficulty of KEM calculations scales more softly than full molecule methods. Although KEM provides accurate energies those energies are not required to satisfy the variational theorem. In this article, KEM is extended to provide a full molecule single‐determinant N‐representable one‐body density matrix. A kernel expansion for the one‐body density matrix analogous to the kernel expansion for energy is defined. This matrix is converted to a normalized projector by an algorithm due to Clinton. The resulting single‐determinant N‐representable density matrix maps to a quantum mechanically valid wavefunction which satisfies the variational theorem. The process is demonstrated on clusters of three to twenty water molecules. The resulting energies are more accurate than the straightforward KEM energy results and all violations of the variational theorem are resolved. The N‐representability studied in this article is applicable to the study of quantum crystallography. © 2017 Wiley Periodicals, Inc. 相似文献
79.
Phase diagram of a water/sucrose monododecanoate (SE)/hexanol system was determined at 30°C. Aqueous micellar, reverse micellar, normal hexagonal liquid crystalline, and lamellar liquid crystalline phases appear in the phase diagram. The change in interlayer spacing and interfacial section area of surfactant in the liquid crystalline phases was investigated by small-angle x-ray scattering. Upon addition of water, the section area and the radius of cylindrical aggregates are almost constant in a hexagonal liquid crystal, whereas the distance between each cylinder is separated on the water-SE axis. The interlayer spacing slightly decreases or is almost unchanged on the surfactant-hexanol axis, because alcohol molecules penetrate into the palisade of bilayers. Although the average section area decreases with increasing alcohol content, each section area of SE and alcohol molecules are kept constant. Since the interfacial section area of alcohol is less than the section area of hydrocarbon chain, the phase transition from lamellar liquid crystal to reverse micelle occurs in an alcohol-rich region. 相似文献
80.
The new dipyrido[3,2-a:2′,3′-c]phenazine (dppz) copper(II) complex, [Cu(tpy)(dppz)]2+, where tpy is 2,2′:6′,2″-terpyridine, has been prepared and fully characterized by spectroscopic methods and single-crystal X-ray diffraction. Its DNA binding and in vitro cytotoxicity have been also studied. The molecular structure shows a distorted trigonal bipyramidal CuN5 coordination geometry around the copper atom. The bidentate dppz ligand binds in the equatorial plane, while tpy exhibits axial-equatorial bonding. The interaction of the complex with DNA has been investigated by electronic absorption, competitive fluorescence titration, linear dichroism, voltammetric techniques and a gel electrophoresis mobility shift assay. It is proposed that the binding mode of the complex to DNA is of an intercalation nature with the planar dppz ligands located between the base pairs of double-stranded DNA.An in vitro cytotoxicity study of the complex on human breast adenocarcinoma (MCF7) cell line by an MTT assay indicates that the title complex may have the potency to act as an effective anticancer drug, with an IC50 value of 4.57 μM (3.62-5.77). 相似文献