Synthesis,Vibrational Spectrum and Structure of the Tetracyanoborate K[B(CN)4]·CH3CN

The new tetracyanoborate K[B(CN)₄]·CH₃CN was synthesized by dissolution of the solvent‐free K[B(CN)₄] in acetonitrile and subsequent careful crystallization. The crystal structure has been determined by single‐crystal X‐ray diffraction. It crystallizes in the orthorhombic space group P2₁2₁2₁ with Z = 4. Some comparisons with related structures are made, and the vibrational spectrum is discussed.     

New Ba5M5−xPtxClO13 (M=Fe, Co) oxychlorides with layered perovskite-related structure

Crystals of Ba₅Fe_5−xPt_xClO₁₃ and Ba₅Co_5−yPt_yClO₁₃ were prepared for x=1.31, 1.51, 1.57, 1.59 and y=0, 0.97 and 1.08 in a BaCl₂ flux and investigated by X-ray diffraction methods. These compounds adopt a 10H perovskite structure built from the stacking of BaO₃ and BaOCl layers in the sequence (BaO₃)₄(BaOCl) with space group P6₃/mmc. The cation sites within the trimeric unit of face-sharing octahedra are occupied by Co or Fe and Pt ions, while the tetrahedral sites formed between BaO₃ and BaOCl layers are only occupied by Fe or Co. Moreover, oxygen stoichiometry indicates an average oxidation state for Co and Fe higher than +III, indicating the stabilization of Co⁴⁺ and Fe⁴⁺.     

Structural and magnetic characterization of Mn3IrGe and Mn3Ir(Si1−xGex): experiments and theory

The structural and magnetic properties of a new ternary Ir-Mn-Ge phase, Mn₃IrGe, as well as the solid solution Mn₃Ir(Si_1−xGe_x), 0?x?1, have been investigated by means of X-ray and neutron powder diffraction, magnetization measurements and first principles calculations. The crystal structure is cubic, of the AlAu₄-type (an ordered form of the β-Mn structure), Z=4, space group P2₁3, and the unit-cell dimension varies linearly with the silicon content. For all compositions, antiferromagnetic ordering is found below a critical temperature of about 225 K. The magnetic structure is noncollinear, as a result of frustrated magnetic interactions on a triangular network of Mn atoms, on which the moments rotate 120° around the triangle axes. The magnitude of the magnetic moment at 10 K is 3.39(4) μ_B for Mn₃IrGe. The theoretical calculations reproduce with very good accuracy the magnitudes as well as the directions of the experimentally observed magnetic moments.     

Zur Elektronenstruktur metallorganischer Komplexe der f‐Elemente. 64 Äußert sich die zwitterionische Natur des Triphenylphosphanoxid‐Liganden auch in seinen spektrochemischen Eigenschaften?

Electronic Structures of Organometallic Compounds of f Elements. 64 Does the Zwitterionic Nature of the Triphenylphosphine Oxide Ligand Manifest itself in its Spectrochemical Properties? The triphenylphosphine oxide mono adducts of the moiety tris(η⁵‐cyclopentadienyl)lanthanide(III) (Ln(Cp)₃; Ln = Pr ( 1 ), La ( 2 )) were synthesized and structurally characterized. The Ln–O distances of these compounds are noticeably shorter than those of the corresponding THF adducts. A crystal field (CF) analysis of the optical spectra of 1 leads to a low absolute value of the quadratic CF parameter which is comparable with those of [Pr(Cp)₃(L)]^? adducts with anionic bases but not with [Pr(Cp)₃(MeTHF)]. Reasons for the latter finding are presented.     

锌的平面三配位[Bu_4N][Zn(SC_6H_2Pr_3~i-2,4,6)_3]·Pr~iOH配合物的合成与晶体结构

在许多重要的金属蛋白中,都存在ⅡB金属与半胱氨酸残基配位的活性中心M(Cys-S)_n.锌、镉、汞与含硫配体的配位化学作为M(Cys-S)_n中心的化学基础,三配位的[M(SR)_3]被认为是金属蛋白中ⅡB金属的一种配位形式.而近年来,Koch报道了平面三配位的锌、镉、汞的硫酚配合物[(n-Pr)_4N][Zn(SC_6HMe_4-2,3,5,6)_3]和[PPh_4][Cd(SC_6H_2Pr_3~i-2,3,6)_3]及[(n-Pr)_4N][Hg(SC_6H_2Pr_3~i-2,4,6)_3]的晶体结构.他们在实验中由于晶体迅速失去溶剂而未能测定以2,4,6-三异丙基硫酚为配体的锌配合物的晶体结构.最近我们合成了这个配合物,并测定了其晶体结构.     

ANN原子参数法预报合金相晶型及晶格常数

运用人工神经网络方法，以二元合金组成元素的电子结构为基本特征，对二元合金相晶型作了区分，进一步对其晶格常数作了预报，结果令人满意。     

Synthese und Kristallstruktur von Blei(II)‐oxidhalogenid‐Alkoholaten mit unterschiedlichen Verknüpfungsvarianten von Pb4O4‐Heterokubaneinheiten

Synthesis and Crystal Structure Determination of Lead(II) Oxide Halide Alcoholates with Different Connectivity of Pb₄O₄ Heterocubane‐like Subunits The reaction of red lead(II) oxide (Litharge) and lead(II) halide (Cl^? and Br^?) with diethylene glycole at a temperature of 180 °C leads to the isotypic compounds [Pb₆(C₄H₈O₃)O₂Cl₆] (1) and [Pb₆(C₄H₈O₃)O₂Br₆] (2) . In a similar synthesis with PbI₂ as educt at temperature of 160 °C the two modifications β‐[Pb₆(C₄H₈O₃)O₂I₆] (3) and α‐[Pb₆(C₄H₈O₃)O₂I₆] (4) were found, whereas at a reaction temperature of 180 °C [Pb₉(C₂H₄O₂)(C₄H₈O₃)O₃I₈] (5) was surprisingly obtained as product. The X‐ray diffraction data show that at a temperature of 180 °C a splitting of the ether took place. The cited compounds show cubane like subunits built by lead and oxygen atoms. These fragments are connected by alkoholate molecules. In 5 additionally an I₆ octahedra centered by lead is observed.     

Solvothermal Synthesis, Crystal Structure and Electrochemical Property of Complex [Co(p-MBA)2(2,2''-bipy)(H2O)]·(H2O)

One novel complex [Co(p-MBA)2(2,2'-bipy)(H2O)]·(H2O) has been synthesized by the reaction of p-methylbenzoic acid with 2,2'-bipyridine in the solvent mixture of water and methanol. It crystallizes in triclinic, space group P-1 with a=0.70479(14), b=1.1211(2), c=1.6718(3) nm, α=103.806(3), β=90.795(3), γ=104.207(3)°, V=1.2399(4) nm3, Mr=512.41, Dc=1.373 g/cm3, Z=2, F(000)=532, μ=0.733 mm-1, R=0.0432 and wR=0.0957. The crystal structural analysis shows that the cobalt atom is coordinated with three oxygen atoms from two p-methylbenzoic acids and one water molecule and two nitrogen atoms from one 2,2'-bipyridine,forming a distorted square-pyramidal coordination geometry. The cyclic voltammetry behavior of the complex is also reported.     

2，4，6－三苯基氧鎓盐分子内旋转受阻对其发光行为的影响

研究了４－位苯基取代基旋转受阻和旋转自由的２，４，６－三苯基氧盐的光物理性质。实验结果表明，当４－位苯基取代基旋转受阻时，氧盐化合物在激发态时引起的分子内极化程度比４－位取代基旋转自由的氧盐化合物大，即在激发态时旋转受阻氧盐化合物发生的分子内电荷转移能力较强；４－位取代基旋转自由的化合物的荧光量子产率随溶剂粘度的增大而有所增大，但旋转受阻化合物在相同的条件下则出现相反的结果。实验结果还表明，４－位取代苯基旋转受阻对化合物的荧光发射不利。     

5,6—二亚甲基双环[2.2.1]庚—2—醇及其衍生物的旋光与构型

从（－）－（１Ｓ，２Ｒ，４Ｓ）－５，６－二亚甲基双环［２．２．１］庚－２－醇（Ｉ）和（－）－（１Ｓ，２Ｓ，４Ｓ）－５，６－二亚甲基双环［２．２．１］庚－２－醇（Ⅱ）出发，合成了它们的醚类和取代苯甲酸酯类光学纯的衍生物。通过［α］Ｄ测定和构型分析，发现它们是含有３个手性碳（Ｃ１，Ｃ２和Ｃ４）的桥环化合物，其旋光性与构型的关系均符合可极化度多级圆球不对称性模型。