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81.
Fabiano Molinos de Andrade Clovis Peppe Werner Uhl 《Journal of organometallic chemistry》2005,690(5):1294-1299
The reaction of bromomethyl-dibromo-indium(III), Br2InCH2Br with dialkylselenides, R1SeR2 (R1 = CH3, R2 = CH2C6H5; R1 = C2H5, R2 = CH2C6H5; R1 = R2 = CH2C6H5) afforded the corresponding dialkylselenonium methylide complexes of indium tribromide, Br3InCH2SeR1R2, which were fully characterized by NMR spectroscopy and single crystal X-ray diffraction studies. 相似文献
82.
A new μ3-O triiron(III) complex [Fe3O(OBz)6(CH3OH)3](NO3)(CH3OH)2 (HOBZ = benzoic acid) has been synthesized, its structure has been determined and variable temperature magnetic susceptility has also been measured. In the molecule, three iron atoms formed an equilateral triangle with μ3-O in center. The fitting to the magnetic susceptibility showed that an intramolecular antiferromagnetic exchange interaction occurred between iron atoms with J=-25.51 cm?1, and a weaker intermolecular autiferromagnetic exchange interaction occurred with zJ' = ?2.30 cm?1. 相似文献
83.
Sabine Schmid 《Journal of solid state chemistry》2003,174(1):221-228
The novel alkaline earth silicate borate cyanides Ba7[SiO4][BO3]3CN and Sr7[SiO4][BO3]3CN have been obtained by the reaction of the respective alkaline earth metals M=Sr, Ba, the carbonates MIICO3, BN, and SiO2 using a radiofrequency furnace at a maximum reaction temperature of 1350°C and 1450°C, respectively. The crystal structures of the isotypic compounds MII7[SiO4][BO3]3CN have been determined by single-crystal X-ray crystallography (P63mc (no. 186), Z=2, a=1129.9(1) pm, c=733.4(2) pm, R1=0.0336, wR2=0.0743 for MII=Ba and a=1081.3(1) pm, c=695.2(1) pm, R1=0.0457, wR2=0.0838 for MII=Sr). Both ionic compounds represent a new structure type, and they are the first examples of silicate borate cyanides. The cyanide ions are disordered and they are surrounded by Ba2+/Sr2+ octahedra, respectively. These octahedra share common faces building chains along [001]. The [BO3]3− ions are arranged around these chains. The [SiO4]4− units are surrounded by Ba2+/Sr2+ tetrahedra, respectively. The title compounds additionally have been investigated by 11B, 13C, 29Si, and 1H MAS-NMR as well as IR and Raman spectroscopy confirming the presence of [SiO4]4−, [BO3]3−, and CN− ions. 相似文献
84.
The molecular and electronic structure of the ground state of peroxyacetyl nitrate (PAN) was calculated by the unrestricted
Hartree-Fock-Roothaan method with the use of the standard 3–21G and 6–31G basis set. The potential curve of the internal rotation
about the peroxide bond of PAN was calculated with the 6–31G basis set. The curve contains two maxima. The ground state of
PAN is characterized by a structure in which groups of atoms adjacent to the peroxide bond lie in planes that are perpendicular
to each other (the dihedral angle ϱ(COON) is 89.9°). The calculated barriers to rotation are 19.6 and 66.8 kJ mol−1.
Translated fromIzvestiya Akademii Nauk. Seriya Khimicheskaya, No. 4, pp. 600–604, April, 1998. 相似文献
85.
D.-G. Chen D.-S. Wu H. Zhang Y.-C. Zhang Y.-J. Gong Z.-G. Kan 《Journal of solid state chemistry》2004,177(11):3927-3933
A novel compound Ba2ZnV2O8 has been synthesized in high temperature solution reaction and its crystal structure has been characterized by means of single crystal X-ray diffraction analysis. It crystallizes in monoclinic system and belongs to space group P21/c with a=7.9050(16), b=16.149(3), , β=90.49(3). It builds up from 1-D branchy chains of [ZnV2O84−]∞, and the Ba2+ cations are located in the space among these chains. The IR spectrum, ultraviolet-visible diffuse reflection integral spectrum and fluorescent spectra of this compound have been investigated. The calculated results of energy band structure by the density functional theory method show that the solid-state compound of Ba2ZnV2O8 is an insulator with direct band gap of 3.48 eV. The calculated total and partial density of states indicate that the top valence bands are contributions from the mixings of O-2p, V-3d, and Zn-3d states and low conduction bands mostly originate from unoccupied antibonding states between the V-3d and O-2p states. The V-O bonds are mostly covalence characters and Zn-O bonds are mostly ionic interactions, and the ionic interaction strength is stronger between the Ba-O than between the Zn-O. The refractive index of nx, ny, and nz is estimated to be 1.7453, 1.7469, and 1.7126, respectively, at wavelength of 1060 nm for Ba2ZnV2O8 crystal. 相似文献
86.
Hans Bürger 《Angewandte Chemie (International ed. in English)》1973,12(6):474-486
In contrast to carbon, silicon fails to form multiple bonds that are stable at room temperature. Consequently molecules in which silicon exhibits coordination numbers (CN) of 1, 2, and 3 may only be obtained at very high or low temperatures. Under these conditions their structural features, including multiple bonds, resemble those of carbon. On the other hand, silicon is capable of forming various hexacoordinated compounds making use of its d orbitals. Nitrogen and oxygen bonded to silicon develop an unusual stereochemistry: planar nitrogen, nearly or completely linear oxygen, and considerable shortening of SiN, SiO, and SiF bonds are specific examples. N(SiR3)2 and CH2SiR3 ligands permit stabilization of unusually low CNs of many metals and give rise to amino and alkyl derivatives of unexpectedly high stability due to the particular electronic, the R3Si group. 相似文献
87.
The mixed‐valent oxotantalate Eu1.83Ta15O32 was prepared from a compressed mixture of Ta2O5 and the metals in a sealed Ta ampoule at 1400 °C. The crystal structure was determined by means of single crystal X‐ray diffraction: space group R3¯, a = 777.2(6) pm and c = 3523.5(3) pm, Z = 3, 984 symmetrically independent reflections, 83 variables, RF = 0.027 for I > 2σ (I). The structure is isotypic to Ba2Nb15O32. The salient feature is a [Ta(+8/3)6O12iO6a] cluster consisting of an octahedral Ta6 core bonded to 12 edge‐bridging inner and six outer oxygen atoms. The clusters are arranged to slabs which are sandwiched by layers of [Ta(+5)3O13] triple octahedra. Additional Ta(+5) and Eu(+2) atoms provide the cohesion of these structural units. Twelve‐fold coordinated Eu(+2) atoms are situated on a triply degenerate position 33 pm displaced from the threefold axis of symmetry. A depletion of the Eu(+2) site from 6 to 5.5 atoms per unit cell reduces the number of electrons available for Ta‐Ta bonding from 15 to 14.67 electrons per cluster. Between 125 and 320 K Eu1.83Ta15O32 is semi‐conducting with a band gap of 0.23 eV. The course of the magnetization is consistently described with the Brillouin function in terms of a Mmol/(NAμB) versus B/T plot in the temperature range 5 K — 320 K and at magnetic flux densities 0.1 T — 5 T. At moderate flux densities (< 1 T) the magnetic moment agrees fairly well with the expected value of 7.94 μB for free Eu (2+) ions with 4f7 configuration in 8S7/2 ground state. Below 5 K, anisotropic magnetization measurements at flux densities B < 1 T point to an onset of an antiferromagnetic ordering of Eu spins within the layers and an incipient ferromagnetic ordering perpendicular to the layers. 相似文献
88.
A series of novel bidentate pyrazolone based Schiff base ligands were synthesized by interaction of 4-benzoyl-3-methyl-1-(4′-methylphenyl)-2-pyrazolin-5-one with various aromatic amines like aniline, o-,m-,p-chloroaniline and o-,m-,p-toluidine in a ethanolic medium. All of these ligands have been characterized on the basis of elemental analysis, IR and 1H NMR data. The molecular geometries of five of these ligands have been determined by single crystal X-ray study. Crystallographic study reveals that these ligands exist in the amine-one tautomeric form in the solid state. NMR study also suggests the existence of the amine-one form in solution at room temperature. Ab initio calculations for representative ligand HL1 has been carried out to know the coordination site of the ligand. Novel vanadium Schiff base complexes of these ligands with general formula [OV(L1–7)2(H2O)] have been prepared by interaction of aqueous solution of vanadyl sulfate pentahydrate with DMF solution of the appropriate ligands. The resulting complexes have been characterized on the basis of elemental analysis, vanadium determination, molar conductance and magnetic measurements, thermo gravimetric analysis, infrared and electronic spectral studies. Suitable distorted octahedral structures have been proposed for these complexes. 相似文献
89.
Preparation, Crystal Structure, and Normal Coordinate Analysis of Linkage Isomeric Pentachloroiodoselenocyanatoosmates(IV). Crystal Structure of trans‐(PPh4)2[OsCl4I(NCSe)] By treatment of the solution of (n‐Bu4N)2[OsCl5I] in dichloromethane with suspended Pb(SeCN)2 the linkage isomers trans‐(n‐Bu4N)2[OsCl4I(NCSe)] ( 1 ) and trans‐(n‐Bu4N)2[OsCl4I(SeCN)] ( 2 ) are formed, which have been separated by ion exchange chromatography on diethylaminoethyl cellulose. The X‐Ray structure determination on a single crystal of trans‐(PPh4)2[OsCl4I(NCSe)] (triclinic, space group P1¯, a = 10.8950(13), b = 11.076(2), c = 20.980(2)Å, α = 96.940(10), β = 98.747(9), γ = 104.419(11)°, Z = 2) reveals, that the nearly linear selenocyanate group in trans position to the iodine atom is coordinated with the Os‐N‐C angle of 171.1°. Based on the molecular parameters of the X‐ray determination ( 1 ) and estimated data ( 2 ) the IR and Raman spectra of both linkage isomers are assigned by normal coordinate analysis. The valence force constants are fd(OsN) = 1.70 und fd(OsSe) = 1.15 mdyn/Å. 相似文献
90.
Two inorganic-organic hybrid solids, Zn2(phen)(HPO3)2 (1) and Zn(phen)(HPO3) (2), have been synthesized under solvothermal conditions in the presence of 1,10-phenanthroline (phen) ligands. Their structures were determined by single-crystal X-ray diffraction and further characterized by FTIR, elemental analysis, powder X-ray diffraction, thermogravimetric analysis and fluorescent spectra. Compound 1 crystallizes in the triclnic system, space group P-1, , , , α=75.609(1)°, β=79.145(2)°, γ=67.157(2)°, , Z=2. Compound 2 is monoclinic, C2/c, , , , β=94.175(4)°, , Z=8. Both structures consist of 1D chains constructed from strictly alternating ZnO4 and HPO3 polyhedra through sharing vertices. The chains are further decorated by Zn-centered complex architectures, [Zn(phen)]2+ for 1 and [Zn(phen)2]2+ for 2. The 2D and 3D supramolecular arrays for 1 and 2 are stably stacked via strong π-π interactions of the phen groups, respectively. 相似文献