Crystal structure and spectral characteristics of {[(C6H5)NH]2C=NH(C6H5)}[B(C6H5)4]·C2H5OH

A novel compound of {[(C₆H₅)NH]₂C=NH(C₆H₅)}[B(C₆H₅)₄]·C₂H₅OH is prepared and examined by single crystal X-ray diffraction. Crystal data: C₄₅H₄₄BN₃O, M = 653.64, monoclinic, space group P2₁/c, unit cell parameters: a = 24.375(2) Å, b = 17.5829(15) Å, c = 18.090(1) Å, β = 105.277(2)°, V = 7479.0(11) ų, Z = 8, d _calc = 1.161 g/cm³, T = 293 K, R ₁ = 0.064. The structure contains two crystallographically independent cations, two anions, and two solvate ethanol molecules. Three types of interactions occur between them: interionic N-H(N)⋯π and N(H)⋯π⋯H(C), π-delocalized system of Ph rings of the anions, and interaction of ions with ethanol molecules N-H⋯O-H(O)⋯π. The compound is characterized by IR and luminescence spectra. At room temperature, the emission intensity grows with time of exposure to UV irradiation. Original Russian Text Copyright ? 2008 by T. M. Polyanskaya, E. A. Il’inchik, V. V. Volkov, M. K. Drozdova, O. P. Yur’eva, and G. V. Romanenko __________ Translated from Zhurnal Strukturnoi Khimii, Vol. 49, No. 3, pp. 512–521, May–June, 2008.     

［C5H4C(CH3)(C3H7)CH2CH=CH2］NdMg2(μ3-OH) (μ3-Cl)(μ2-Cl)3(THF)4Cl的合成和晶体结构分析

用X-射线衍射法测定了［C₅H₄C(CH₃)(C₃H₇)CH₂CH=CH₂］NdMg₂(μ₃-OH)(μ₃-Cl)(μ₂-Cl)₃(THF)₄Cl的晶体结构。它属三斜晶系,空间群为<     

双核Fe配合物[(η5-C5H4)C6H10(C4H3S)Fe(CO)2]2的合成和晶体结构

由侧链带有噻吩的环戊二烯基配体C5H5C6H10C4H3S与Fe(CO)5在二甲苯中加热回流,合成了1个新颖的四羰基二铁配合物[(η5-C5H4)C6H10(C4H3S)Fe(CO)2]2。通过元素分析、IR、1H NMR对其结构进行了表征,用X-射线单晶衍射确定了其结构。X-射线单晶衍射表明配合物中有2个桥羰基和2个端羰基,Fe-Fe的键长为0.25465(10)nm。     

夹心化合物Ni(C5H5)2的Xα研究

用Xα方法计算了Ni(C5H5)2的电子能级与归一化电荷,讨论了夹心化合物成键的特点,并用过渡态方法分析Ni(C5H5)2的光电子能谱及紫外可见吸收光谱,结果与实验相符。     

RE(C5H8NS2)3(C12H8N2)的标准摩尔生成焓

在无水乙醇中, 使低水合氯化稀土 (RE = Ho, Er, Tm, Yb, Lu) 与吡咯烷二硫代氨基甲酸铵 (APDC)和1,10-菲咯啉 (o–phen•H₂O) 反应, 制得其三元固态配合物. 用化学分析和元素分析确定它的组成为RE(C₅H₈NS₂)₃(C₁₂H₈N₂) (RE = Ho, Er, Tm, Yb, Lu). IR光谱说明RE³⁺ 分别与3个PDC^–的6个硫原子双齿配位, 同时与o–phen的2个氮原子双齿配位, 配位数为8. 用精密转动弹热量计测定了它们的恒容燃烧热△_cU分别为(-16788.46 ± 7.74), (-15434.53 ± 8.28), (-15287.80 ± 7.31), (-15200.50 ± 7.22)和(-15254.34 ± 6.61) kJ•mol^-1; 并计算了它们的标准摩尔燃烧焓△_cH_m^θ和标准摩尔生成焓△_fH_m^θ分别为( -16803.95 ± 7.74), (-15450.02 ± 8.28), (-15303.29 ± 9.28), (-15215.99 ± 7.22), (-15269.83 ± 6.61) kJ • mol^-1和 (-1115.42 ± 8.94), (-2477.80 ± 9.15), (-2619.95 ± 10.44), (-2670.17 ± 8.22), (-2650.06 ± 8.49) kJ•mol^-1.     

CH3F与C2H3反应机理的理论研究

采用密度泛函B3LYP/6-311G(d,p)方法对CH3F与C2H3的反应体系进行了理论研究,获得了反应的势能面信息及可能的微观机理.在QCISD(T)/6-311++G(d,p)水平上精确计算了各反应物种的单点能.结果表明,除抽提氢反应外,标题反应还存在抽提氟(R1)、消氟化氢(R2)、消氢(R3)和自由基形成(R4)四类反应.在QCISD(T)/6-311++G(d,p)//B3LYP/6-311G(d,p)水平上,R1,R2,R3和R4反应的能垒分别是163.9,152.2,209.8和224.2kJ·mol-1,相应反应能为-56.6,-164.3,-2.7和-156.0kJ·mol-1,所有反应均放热,为热力学允许的反应.     

配合物[Mn(C13H8N2OBr)2(C5H5N)2]·3C5H5N的结构与磁性研究

The complex [Mn(C₁₃H₈N₂OBr)₂(C₅H₅N)₂]·3C₅H₅N has been synthesized and characterized by X-Ray diffraction, IR and variable temperature (～10 to ～278K) magnetic susceptibility. X-Ray diffraction result for the single crystal shows that the crystal belongs to monoclinic, space group P2₁/c, a=1.0969(3)nm, b=2.0903(5)nm, c=2.0481(6)nm, β=97.366(6), V=4.657(2)nm³, Z=4, D_c=1.47g·cm^-3。     

Structural Dynamics of Isomorphic Substitution in N,N′-Diallylbenzimidazolium Copper Halide π-Complexes [C7H5N2(C3H5)2]+[Cu2Cl3?xBrx]? (x=0, 1.60, 2.33, 3)

Two new -complexes of copper(I) halides with the 1,3-diallylbenzimidazolium cation, [C₇H₅N₂(C₃H₅)₂]⁺[Cu₂Cl_1.40Br_1.60]^– and [C₇H₅N₂(C₃H₅)₂]⁺[Cu₂Br₃]^–, have been synthesized and structurally defined (space group P2 ₁/c for both; a = 22.094(6), b = 9.272(8), c = 9.22(1) , = 118.26(4)° and a = 22.267(5), b = 9.311(3), c = 9.263(2) , = 117.51(2)°). The mutual effects of chlorine–bromine substitution and the efficiency of -interactions are discussed based on XRD data for these two compounds and for the compounds [C₇H₅N₂(C₃H₅)₂]⁺[Cu₂Cl₃]^– and [C₇H₅N₂(C₃H₅)₂]⁺[Cu₂Cl_0.67Br_2.33]^– studied previously.     

Isomerism of [FeMM′(μ3-Q)(CO)7CpCp′] heterometallic clusters (Q = Se, Te; M, M′ = Mo, W; Cp = η5-C5H5; Cp′ = Cp, η5-C5(CH3)5) in solids

The crystal structures of three cluster compounds: [(µ-H)Fe₂Mo(µ₃-Te)(CO)₈Cp*], [FeMo₂(µ₃-Te)(CO)_7x Cp*₂], and [FeMoW(µ₃-Te)(CO)₇CpCp*], where Cp = ⁵-C₅H₅, Cp* = ⁵-C₅ (CH₃)₅, have been investigated. In the cluster with a tetrahedral {FeMo₂Te} core, one can observe positional isomerism of the carbonyl and cyclopentadienyl ligands with respect to the plane through the Fe and Te atoms and the center of the Mo₂bond, resulting in two mirror isomers in the racemic crystal. In the cluster with the {FeMoWTe} core, additional chirality causes the formation of four diastereoisomers. Earlier, the structure of the [FeMoW(µ₃-Se)(CO)₇Cp] cluster with Mo and W atoms coordinated to identical Cp-ligands has been structurally defined. In this crystal, statistical disordering of Mo and W over the metal positions is observed. In the [FeMo(Cp*)W(Cp)(µ₃-Te)(CO)₇] cluster studied here, the Mo and W atoms are coordinated to different cyclopentadienyl ligands. Due to this, two of four diastereoisomers were isolated as ordered racemic crystals; the other two are nonexistent for steric reasons.Original Russian Text Copyright © 2004 by A. V. Virovets, S. N. Konchenko, P. S. Yuferov, and D. FenskeTranslated from Zhurnal Strukturnoi Khimii, Vol. 45, No. 3, pp. 522–527, May–June 2004.     

Synthesis and crystal structure of π-complex of copper(I) with 1-allylbenzimidazolium cation [C7H5N2H(C3H5)]+ [Cu3Cl4]?

Single crystals of [C₇H₅N₂H(C₃H₅)]⁺[Cu₃Cl₄]^– were obtained for the first time by ac electrochemical synthesis from 1-allylbenzimidazolium and copper(II) chlorides in ethanol and structurally characterized. The unit cell parameters are a=8.6755(9) , b=8.846(1) , c=10.4540(7) , =85.36(1)°, =70.529(7)°, =83.29(1)° , V=750.5(3) ³, space group P , R(F)=0.0551. In the -complex, the copper and chlorine atoms form complicated infinite chains along the x axis. The 1-allylbenzimidazolium cation functions as an original bridge: it is coordinated by the Cu atom of one cuprous-chloride chain through the C=C bond of the allyl group and forms a N-HCl hydrogen bond with another inorganic chain through the N atom of the imidazole ring. The trigonal pyramidal environment of the Cu(1) atom includes three Cl atoms and the C=C bond; the environments of the Cu(2), Cu(3), and Cu(3a) are composed only of chlorine atoms. The positions of the Cu(2) and Cu(3a) atoms are partially disordered, which is manifested by the high thermal parameters for the Cu(2) atom and by the splitting of another copper atom into two equally occupied positions Cu(3) and Cu(3a).Translated from Koordinatsionnaya Khimiya, Vol. 31, No. 3, 2005, pp. 199–203.Original Russian Text Copyright © 2005 by Goreshnik, Schollmeyer, Myskiv.This revised version was published online in April 2005 with a corrected cover date.This revised version was published online in April 2005 with a corrected cover date.     

Functionalised tetraarylstannanes Sn[C6H4-R]4 (R=-CH(CH2O)2, -CHO, -COOH, -CHN-NH-C6H3-2,4-(NO2)2, -CH2OH, -CO-NH-CH2-COO-CH3, -CH[N(C2H4)2O]2)

Reaction of tin tetrachloride with the appropriate Grignard reagent gave Sn[C₆H₄-CH(OCH₂)₂]₄ (2), which was transformed to Sn[C₆H₄-CHO]₄ (3) and its hydrazido and amino derivatives Sn[C₆H₄-CHN-NH-C₆H₃-2,4-(NO₂)₂]₄ (5) and Sn{C₆H₄-CH[N(C₂H₄)₂O]₂}₄ (8). Oxidation of (3) produced Sn[C₆H₄-COOH]₄ (4) while reduction of (3) gave Sn[C₆H₄-CH₂-OH]₄ (6). From the acid 4, an amino acid Sn[C₆H₄-CO-NH-CH₂-CO-OCH₃]₄ (7) could be obtained by reaction with the methyl ester of glycine. All compounds were isolated in pure form with yields of 40-64% and were characterised by spectroscopic means (heteronuclear NMR) or by X-ray structure determination (3).     

Complexation between N-allylmorpholinium derivatives and copper(I) halides. Synthesis and crystal structure of π-complex {[C4H8ONH(C3H5)]+}2[Cu2Cl4]2?

Copper(I) -complex {[C₄H₈ONH(C₃H₅)]⁺}₂[Cu₂Cl₄]^2– (I) was obtained by ac electrochemical synthesis from N-allylmorpholine hydrochloride and copper(II) chloride in ethanol and structurally characterized. In structure I, copper and chlorine atoms form unique noncentrosymmetric Cu₂Cl ₄ ^2– fragments. Both crystallographically independent N-allylmorpholinium cations are involved in the -interaction and are coordinated by the copper atom through the C=C bond of the allyl group. The trigonal pyramidal environment of the Cu(1) atom is composed of three chlorine atoms and the C=C bond, while the Cu(2) atom coordinates two chlorine atoms and the C=C bond forming a planar triangle. The extremely strong N-CCl hydrogen bond (HCl 2.2 ) prevents the Cl(1) atom from acting as a bridge and favors the formation of fragments Cu₂Cl ₄ ^2– .__________Translated from Koordinatsionnaya Khimiya, Vol. 31, No. 4, 2005, pp. 306–310.Original Russian Text Copyright © 2005 by Goreshnik, Davydov, Myskiv.     

Unusual selectivity in photooxygenation of alkanes by air in CH3CN solutions catalyzed by CrCl3?C6H5CH2N(C2H5)3Cl

A new system CrCl₃–C₆H₅CH₂N(C₂H₅)₃Cl–CH₃CN for photooxygenation of alkanes is suggested. Unlike metal chlorides and oxocomplexes, it oxidizes alkanes to produce ketones and small amounts of alcohol. Adding of benzene, methylene chloride or ethanol to the cyclohexane solution rises the oxygenation rate and changes the ketone/alcohol ratio. With small amounts of hydroquinone the formation rate of cyclohexanone (but not of cyclohexanol) sharply decreases. Kinetic isotope effect in the oxidation of C₆H₁₂ and C₆D₁₂ is 1 for cyclohexanol and 2.9 for cyclohexanone. Cyclohexanol formation is assumed to follow a mechanism that does not involve free radicals. Free radicals can participate in the route toward ketone.

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CrCl₃–C₆H₅CH₂N(C₂H₅)₃Cl–CH₃CN . , . , /. ( ) . C₆H₁₂ C₆D₁₂ 1 2,9 . , , . , .

     

Kinetics of the radical reactions in pulse radiolyzed RHF — CO2(SF6)-O2-NO gaseous mixtures; RHF = CH3CH2F, CH3CHF2, CH3CF3, CH2FCF3

The kinetics of the peroxy radicals RHFO₂ reactions with NO has been studied by using pulse radiolysis and UV absorption spectroscopy. The rate constants of interaction of oxygen atoms with NO − k ₂ = 2.2±0.2·10⁻¹² cm³·s⁻¹ and NO₂ − k ₃ = 2.1±0.2·10⁻¹¹ cm³·s⁻¹ were found in agreement with the literature values. The bath gases (SF₆ or CO₂) have got minor effect on the rate constants of RHFO₂+NO→NO₂+prod. reactions; RHFO₂ = CH₃CH₂O₂, CH₃CHFO₂, CH₃CF₂O₂, CF₃CH₂O₂, CF₃CHFO₂. The obtained rate coefficients are in the scope of the literature values, although they are lower than those recommended in NIST database. The reasons are discussed.     

New aromatic pentafluoro-λ-sulfanyl (SF5) derivatives, m-SF5(CF2)2C6H4X: (X = N3, Br, OC(O)CHCH2, CHCH2)

Preparation of the following new m-SF₅CF₂CF₂C₆H₄X derivatives has been achieved: X=N₃(2), Br(3), OC(O)CHCH₂(4), CHCH₂(5). The compounds were characterized by their respective IR, NMR, mass spectra (MS) and high resolution mass spectrometry (HRMS). An improved yield of SF₅(CF₂)₂C₆H₅ (1) is also reported along with the synthesis of the polyacrylate (6) and polystyrene (7) from their respective monomers.     

Toluene-solvated zinc dimethyldithiocarbamate adduct with piperidine [Zn{NH(CH2)5}{S2CN(CH3)2}2] · 2C6H5CH3: Synthesis, structure, and thermal properties

A solvated form of zinc dimethyldithiocarbamate adduct with piperidine of the composition [Zn{NH(CH₂)₅}{S₂CN(CH₃)₂}2] · 2C₆H₅CH₃ (I) was synthesized. The structure and thermal properties of the adduct were studied by X-ray crystallography and simultaneous thermal analysis (STA). The structure of compound I is characterized by the presence of a system of channels populated by solvating toluene molecules (structural type of lattice clathrates). The central zinc atom coordinates two dithiocarbamate ligands and a piperidine molecule (zinc coordination number CN_Zn = 5). The zinc polyhedron geometry is intermediate between a tetragonal pyramid (TP) and trigonal bipyramid (TBP); the contributions of the TP and TBP components were evaluated from the X-ray diffraction data. The STA study of the thermal properties of I has shown that the weight loss occurs in three steps and includes desorption of solvating toluene molecules, then, desorption of coordinated piperidine molecules, and thermolysis of the dithiocarbamate moiety of the complex with formation of a zinc sulfate powder.     

[Ce(NO3)5H2O]·(C3H5N2)2的合成、晶体结构及热分析

Colorless crystal, [Ce(NO₃)₅H₂O]·(C₃N₂H₅)₂, has been obtained from the reaction of Ce(NO₃)₃ with imdazole in the aqueous solution and its crystal structure has been determined by single crystal X-ray diffraction techniques.The crystal belongs to triclinic, space group P1. The cell parameters are: a = 0.7489(1) um, b = 0.7914(2) nm, c = 1.8139(3) nm, a = 89.39(2)°, β = 89.37(l) °,γ = 63.18(2)°, Dc = 2.1g·cm^-3, Z = 2, R = 0.0319.In the compound, all of five nitrates are bidentate and one molecule of water is monodentate, the coordination number of Ce (Ⅲ) is 11.The processes of thermal decomposition of the compound was proposed by its TGcurve.     

Unusual ion UO4? formed upon collision induced dissociation of [UO2(NO3)3]?, [UO2(ClO4)3]?, [UO2(CH3COO)3]? ions

The following ions [UO₂(NO₃)₃]⁻, [UO₂(ClO₄)₃]⁻, [UO₂(CH₃COO)₃]⁻ were generated from respective salts (UO₂(NO₃)₂, UO₂(ClO₄)₃, UO₂(CH3COO)2) by laser desorption/ionization (LDI). Collision induced dissociation of the ions has led, among others, to the formation of UO₄ ⁻ ion (m/z 302). The undertaken quantum mechanical calculations showed this ion is most likely to possess square planar geometry as suggested by MP2 results or strongly deformed geometry in between tetrahedral and square planar as indicated by DFT results. Interestingly, geometrical parameters and analysis of electron density suggest it is an U^VI compound, in which oxygen atoms bear unpaired electron and negative charge.