Tieftemperatur-flüssigphasefluorierung von pentafluorphenyl-element-Verbindungen. Darstellungen und eigenschaften von (C6F5)3AsF2, (C6F5)3SbF2, (C6F5)2SeF2, (C6F5)2SeO,C6F5TeF3 und Cs[(C6F5)3EF3] (E = As,Sb) [1]

The fluorination reactions of (C₆F₅)₃E (E = As, Sb) with elemental flourine yield (C₆F₅)₃EF₂ in high yields. From the reactions of (C₆F₅)₃EF₂ with CsF the new salts Cs[(C₆F₅)₃EF₃] are obtained. (C₆F₅)₂SeF₂ and C₆F₅TeF₃ are formed for the first time by reacting (C₆F₅)₂SeF and (C₆F₅)₂TeF₂ with elemental flourine and XeF₂, respectively. (C₆F₅)₂SeF₂ rapidly reacts with glass, and the new compound (C₆F₅)₂SeO is isolated. The preparations, properties and ¹⁹F NMR spectra of the new compounds are described.     

用分子束研究.F(^2P)与CH3F和CH3Cl的化学反应

近年来, 我们在研究含氟烯烃和烷烃的红外激光诱导氧化和氯化反应的基础上, 深入研究了红外激光诱导卤代烷烃的脱卤化氢并生成: CF2卡宾和:CFCF3卡宾的反应[1-4]以往的研究往往是根据反应产物推论反应机理, 认为在反应过程中存在着卡宾中间体,但在实验中未能直接检测到. Kakimoto[5,6]曾报道过在流动体系中测到了.F+CH3F和.F+CH3Cl反应中:CHF和:CHCl的激光荧光激发谱, 但没有讨论卡宾形成的机理.Hirota[7]在讨论.F+CH3F反应时, 认为:CHF可能由攫氢过程产生而对于.F+CH3Cl反应同时生成:CHF和:CHCl未做说明. 本实验中用扩散分子束代替了流动反应体系, 从而大大减少了产物和反应物气体分子间的猝灭过程, 获得了信噪比大而清晰的图谱, 由此确证了:CHF和:CHCl的存在, 说明了.F+CH3Cl反应中自由基攫氢过程和偶合反应过程共存的反应历程. 这一结论对红外激光诱导一碳卤代宾化学反应机理研究有重要参考意义.     

Antimony(III) Oxofluorides α-Sb3O2F5 and β-Sb3O2F5: Synthesis and Crystal Structures

The conditions for the synthesis of two polymorphous forms of antimony(III) oxofluoride Sb₃O₂F₅ from aqueous solutions are established. The crystal structure of a new polymorphous modification -Sb₃O₂F₅ is determined (monoclinic crystals with a = 6.9548(6) Å, b = 9.1043(7) Å, c = 20.336(2) Å, = 94.167(2)°, V = 1284.2(2) ų, Z = 8, (calcd) = 5.092 g/cm³, F(000) = 1712, space group P2₁/n) and the structure of -Sb₃O₂F₅ is refined. The geometric characteristics of crystal structures of antimony(III) oxofluorides SbOF (L- and -forms) are compared with those of Sb₃O₂F₅ (- and -forms).     

Fluorine-Containing Furan-3(2Н)-Ones in Reactions with Binucleophiles: CF3vs C2F5

Chemistry of Heterocyclic Compounds - Five- and six-membered fluorine-containing azaheterocycles were synthesized based on available furan-3(2H)-ones, and the influence of the nature of the...     

Two binuclear complexes containing the enrofloxacinate anion: Cd2(C19H21N3O3F)4(H2O)2 · 4H2O and Pb2(C19H21N3O3F)4 · 4H2O

The syntheses and crystal structures of the closely related but non-isostructural Cd₂(C₁₉H₂₁N₃O₃F)₄(H₂O)₂?·?4H₂O (1) and Pb₂(C₁₉H₂₁N₃O₃F)₄?·?4H₂O (2) are described, where C₁₉H₂₁N₃O₃F^? is enrofloxacinate (enro). Both compounds contain centrosymmetric, binuclear, neutral complexes incorporating a central diamond-shaped M₂O₂ (M?=?Cd, Pb) structural unit. The Cd²⁺ coordination polyhedron in 1 is a CdO₆ trigonal prism, including one coordinated water. The Pb²⁺ coordination polyhedron in 2 can be described as a very distorted square-based PbO₅ pyramid, although two additional short Pb?···?O (<3.1?Å) contacts are also present. In the crystal of the cadmium complex, O–H?···?O hydrogen bonds lead to a layered structure. In the lead compound, O–H?···?O and O–H?···?N interactions lead to chains in the crystal. Crystal data: 1: C₇₆H₉₆Cd₂F₄N₁₂O₁₈, M _r?=?1766.45, triclinic, P 1, a?=?12.185(2)?Å, b?=?12.306(3)?Å, c?=?14.826(3)?Å, α?=?68.15(3)°, β?=?70.28(3)°, γ?=?86.11(3)°, V?=?1938.2(7)?ų, Z?=?1, T?=?298 K, R(F)?=?0.030, wR(F ²)?=?0.079. 2: C₇₆H₈₈F₄N₁₂O₁₆Pb₂, M _r?=?1920.00, triclinic, P 1, a?=?12.0283(4)?Å, b?=?12.7465(4)?Å, c?=?13.0585(4)?Å, α?=?83.751(1)°, β?=?74.635(1)°, γ?=?81.502(1)°, V?=?1904.3(1)?ų, Z?=?1, T?=?298?K, R(F)?=?0.021, wR(F ²)?=?0.049.     

Mixed Amidohalotantalates [Ta(NMe2)3X3]– (X = F,Cl)

Russian Journal of Coordination Chemistry - The anionic tantalum complex (ItBuH)[Ta(NMe2)3Cl3] (I) is synthesized by the reaction of [Ta(NMe2)3Cl2]2 with N-heterocyclic carbene ItBu and is isolated...     

一种新型杂化单晶[Ga3(PO4)3F2]H3O·(H3NCH2CH2)2NH2的合成与结构表征

自从系列磷酸铝微孔晶体首次被报道以来, 空旷骨架磷酸盐化合物的合成取得了长足进展[1,2]. 其中, 空旷磷酸镓骨架化合物以其丰富的拓扑连接方式成为研究的热点之一[1,3,4]. 特别是向水热合成体系中引入氟离子, 导致了新颖微孔磷酸镓化合物的不断出现, 如磷酸镓-CLO[5], 磷酸镓MIL-31[6]等化合物. 目前, 合成实验表明, 乙烯胺类化合物(如二乙烯三胺)因其构象变化复杂, 可以诱导出多种新颖空旷骨架磷酸盐[7～9]. 由于氟离子可以同磷酸镓骨架中的镓原子配位, 进而改变骨架拓扑连接方式和电荷分布, 因此氟原子与二乙烯三胺协同作用可能获得新颖的无机骨架与导向剂的自组装模型.     

多通道反应O(3P)＋CH2F的理论研究

用密度泛函理论研究了氧原子与氟代甲基自由基的反应.反应中出现的所有物种的平衡构型用B3LYP方法在6-311＋＋G（2d, 2p）基组水平上进行了优化，同时对各物种进行了频率分析；在同一理论水平上计算了各反应通道的势能面变化，分析了反应物、中间体、过渡态、产物的振动模式随反应途径的变化关系，阐明了该多通道反应的反应机理.     

Sr_3Ca_2(PO_4)_3X:Eu~(2+)(X=F,Cl,Br)的光激励发光与F色心

研究了Eu~(2+)激活的Sr_3Ca_2(PO_4)_3X晶体中的F色心及光激励发光。讨论了不同卤离子对F色心及其能级结构的影响。探讨了在X光辐照下和光激励发光过程中Eu~(2+)的价态变化及光激励发光过程的机理。     

CX3NO2(X=F,Cl)分子结构的稳定性

分子CF_3NO_2(1)、CF_2CINO_2(2)、CFCl_2NO_2(3)和CCl_3NO_2(4)在光化学和大气化学中是一类重要的分子。虽然它们的许多性质被广泛研究,但是从理论上尤其是ab initio分子轨道法对它们分子结构和化学键的研究报导极少。本文在ab initio/STO-3G水平上,全构型优化,系统地研究了这类分子的结构和各种构型的稳定性,并与实验以及CX_3NO(X=F,Cl)的结构进行了比较。计算采用Gaussian-82程序。在VAX-8350计算机上完成。结果和讨论分子各种稳定构型的键长、键角、Hartree-Fock能量、电荷密度及偶极矩列于表1至表3。     

Synthesis and Structure of Bismuth Tris(3-Methylbenzoate) [Bi(O2CC6H4CH3-3)3]∞ and Phenylbismuth Bis(3,4,5-Trifluorobenzoate) [PhBi(μ-O2CC6H2F3-3,4,5)(O2CC6H2F3-3,4,5)]2

Bismuth tris(3-methylbenzoate) [Bi(O₂CC₆H₄CH₃-3)₃] (I) and phenylbismuth bis(3,4,5-trifluorobenzoate) [PhBi(-O₂CC₆H₂F₃-3,4,5)(O₂CC₆H₂F₃-3,4,5)]₂ (II) were synthesized by reacting triphenylbismuth with 3-methylbenzoic and 3,4,5-trifluorobenzoic acids. Coordination numbers of bismuth atoms in I and II are 9 and 6, respectively; carboxylate ligands function as bi- and tridentate ligands. The Bi-O distances in compound I vary in the range of 2.218(3)-3.202(4) Å. The Bi-O and Bi-C bond lengths in II are 2.301(2)-2.674(2) and 2.223(3) Å, respectively.     

Ein neuer koordinationstyp bei acyclischen phosphaalkenen: F3CPC(F)NMe2 als (η1-μ2) 4e-donator

The chromium complex Cr(CO)₅[F₃CPC(F)NMe₂] (2) in chloroform solution is slowly transformed at room temperature to give the binuclear system [(CO)₅Cr]₂[F₃CPC(F)NMe₂] (3) besides the C-amino substituted phosphaalkene F₃CPC(F)NMe₂ (1). The yield of this process amounts to 21% within 6 months. The X-ray diffraction analysis of 3 reveals a so far unknown coordination mode of acyclic phosphaalkenes: 1 operates as (η¹-μ₂) 4e donor.     

STRUCTURE OF [W(H)_2(F)(OH_2)(PMe_2)_4]F

<正> Mr = 546.3, orthorhombic, space group Cmc21, a = 14.223(4), b = 12.907(3), c = 12.343(4) A, V = 2265.746 A3, Z = 4, DC = 1.601 Mg.m-3, λ= 0.7106 A, μ(MoK(?)) = 56.86 cm-1, F(OOO) = 1048. Final R = 0.044 for 1937 observed reflections. Cation [W(H)2(F)(OH2)(PMes)4]4 has a mirror symmetry, an equatorial belt of four PMe3 groups and mutually syn fluoride and water Ugands. The mean W-P length is 2.462 (A) and P-C 1.83 (A). From the dimensions of the metal, fluoride and water system ( W(1)-F(1) = 2.08(1), W(1)-0(1) - 2.084(9), F(2)-O(1) = 2.59(2) A and F(2)-W(1)-O(1) - 76.7(4)°) an in-terligand hydrogen bond was assumed. The ligand water molecule also makes an H-bonded contact with the fluoride counter ion.     

Na3V2(PO4)2O2F的合成及其在钠离子电池中的应用

目前,合成Na3V2(PO4)2O2F(NVPF)材料的方法包括高温固相法、水热法、溶剂热法等,这些方法均不利于该材料的大规模工业化生产.本文开发了温和的低温共沉淀法合成NVPF材料,该材料首次放电容量为105.6 mAh·g-1,首次效率为90.16％.经过简单的热处理过程,可以有效去除由于液相合成带来的结晶水以及吸...     

New polynuclear molecular ferromagnetic complex {Co3((η2-NH2)2C6H2Me2)2(μ-OOCCMe3)2(η1-OOCCMe3)2(η2-OOCCMe3)2(HOOCCMe3)2}{Co((η2-NH2)2C6H2Me2)2(η1-OOCCMe3)2}

Russian Chemical Bulletin -     

Theoretical studies of the reactions of Cl atoms with CF3CH2OCH n F(3−n) (n = 1, 2, 3)

This paper presents the theoretical studies of the reactions of Cl atoms with CF₃CH₂OCH₃, CF₃CH₂OCH₂F and CF₃CH₂OCHF₂ using an ab initio direct dynamics theory. The geometries and vibrational frequencies of the reactants, complexes, transition states and products are calculated at the MP2/6-31+(d,p) level. The minimum energy path is also calculated at same level. The MC-QCISD method is carried out for further refining the energetic information. The rate constants are evaluated with the canonical variational transition state theory (CVT) and CVT with small curvature tunneling contributions in the temperature range 200–1,500 K. The results are in good agreement with experimental values.     

B(C6F5)3-Catalyzed Aza-Friedel–Crafts Reaction of Indolizines with 2-Aryl-3H-indol-3-ones

A Friedel–Crafts reaction of indolizines with 2-aryl-3H-indol-3-ones catalyzed by B(C₆F₅)₃ is described. This protocol gives access to indolizine derivatives that are valuable building blocks in synthetic and pharmaceutical chemistry. The reaction proceeds under mild conditions, affording various C2-quaternary indolin-3-ones based on indolizine with high yields and regioselectivities. Moreover, the synthetic transformations of the target products were realized by N-methylation and trifluoromethane sulfonation.     

RbLn2F7的水热合成及RbLn2F7:Eu3+(Ln=Gd,Y)的VUV光谱

利用水热方法合成出RbLn2F7（Ln=Gd，Y，Er，Yb和Lu），均为六方RbEr2F7型结构。掺杂Eu^3＋离子样品的光谱表明水热产物中氧杂质含量极低。在RbGd2F7：Eu^3＋（0．5mol％）的激发光谱中只观测到Gd^3＋离子f-f跃迁，Eu^3＋离子的激发跃迁很弱。激发Gd^3＋离子到^6IJ能级后，观测到Eu^3＋离子的特征发射，Gd^3＋离子与Eu^3＋离子之间存在能量传递过程。Eu^3＋离子的^5D0→^7F1和^5D0→F2跃迁发射较强，表明稀土离子在六方HbLn2F7中处于非中心对称的格位。     

Tetranuclear bismuth complexes Bi4(O)2(O2CC6H2F3-3,4,5)8 · 2C6H6 and Bi4(O)2(O2CC6H2F3-3,4,5)8 · 2C6H4Me2-1,4: Synthesis and structures

X-ray diffraction study of tetranuclear organobismuth complexes Bi₄(O)₂(O₂CC₆H₂F₃-3,4,5)₈ · 2⁶-C₆H₆ and Bi₄(O)₂(O₂CC₆H₂F₃-3,4,5)₈ · 2(C₆H₄Me₂-1,4) revealed four Bi atoms connected through the bridging carboxylate ligands and the O atoms. The coordination sphere of the terminal Bi atoms includes the chelate carboxylate ligand and the 6-arene molecule. The bridging O atoms are tricoordinated, the distances between the terminal Bi atom and the center of benzene molecule (1,4-dimethylbenzene) are 3.024 Å(3.131 Å).Translated from Koordinatsionnaya Khimiya, Vol. 31, No. 1, 2005, pp. 4–11.Original Russian Text Copyright © 2005 by Sharutin, Egorova, Sharutina, Ivanenko, Adonin, Starichenko, Pushilin, Gerasimenko.