Synthesis, structures and properties of hydrolytic Al(III) aggregates and Fe(III) analogues formed with iminodiacetate-based chelating ligands

Both Al(III) and Fe(III) display a rich hydrolytic chemistry which can lead to the formation of a variety of aggregated oxo and hydroxo-bridged aggregates. The formation, structures and properties of these species are important in defining the availability and reactivity of these species in aqueous environments such as are found in biological systems and the environment. Although there are many similarities in the behaviour of the Al³⁺ and Fe³⁺ ions there are also some important differences between these two metal ions which can lead to a divergence in their chemistries. These considerations are discussed and illustrated with reference to 16 Al(III) and Fe(III) compounds, which have been crystallographically characterised, and which form in aqueous environments in the presence of chelating ligands containing the iminodiacetate functionality.     

R、S-三[N-(邻-氧α-萘亚甲基)-α-苯乙胺]合钴的合成、晶体结构及分子绝对构型

合成了R,S一三[N-(邻-氧α-萘亚甲基)-α-苯乙胺]合钴。x射线单晶衍射衍射测定了晶体结构及分子的绝对构型。晶体属正交晶系,D_2~4-P2_12_12_1空间群,晶胞参数:α=12.587(3),b=14.166(3),c=25.652(14)(?),v=4574.2(?)~3,z=4。用重原子法及差值Fourier合成解出结构,最后的R值为0.074。利用Co~( )对CuKa反常散射测定了分子的绝对构型。Co~( )为六配位,d~2sp~3杂化近正八面体构型。     

Tetraphenylphosphonium-tetradecachlorotetraarsenat(III), (PPh4)2As4Cl14

Tetraphenylphosphonium Tetradecachlorotetraarsenate(III), (PPh₄)₂As₄Cl₁₄ The title compound was obtained by reaction of As₄S₄, PPh₄Cl and chlorine in dichloromethane. According to its X-ray crystal structure analysis, the As₄Cl ion can be described as an association product of two AsCl₄^? units and two AsCl₃ molecules. The As atoms and ten Cl atoms are approximately in a plane, the remaining four Cl atoms alternately take positions above and below this plane. The As atoms have distorted ψ octahedral coordination.     

Kristall- und Molekülstruktur von fac-Trichloro-tris(dimethylsulfoxid)bismut(III) BiCl3(DMSO)3

Crystal and Molecular Structure of fac-Trichloro-tris(dimethyl sulfoxide)bismuth(III) BiCl₃(DMSO)₃ Crystals of the known, although structurally not characterized title compound were fortuitously obtained from a reaction mixture containing (CH₃)₃SiN(SO₂CH₃)₂, BiCl₃, DMSO, CH₂Cl₂ and CH₃NO₂. Crystallographic data (at ?130°C): triclinic, space group P1 1, a = 816.1(5), b = 885.1(6), c = 1 360.6(8) pm, α = 77.58(3), β = 77.39(3), γ = 64.42(3)°, U = 0.8569 nm³, Z = 2. The DMSO ligands are bound through oxygen to the Bi atom. Important bond distances and angles in the resulting fac-octahedral complex are as follows: Bi? Cl 258.9, 261.0, 263.0, Bi? O 242.6, 245.7, 246.1 pm; Cl? Bi? O (trans) 170.3, 170.6, 176.9, Cl? Bi? Cl 94.6, 94.7, 96.0, O? Bi? O 81.7, 85.4, 87.9, Cl? Bi? O (cis) in the range 87.2–92.6, Bi? O? S 123.4, 126.1, 129.6°.     

Synthesis and characterization of Pr(III), Nd(III) and Er(III) complexes with 2,6-pyridinedimethanol

The reactions of Ln(NO₃)₃?6H₂O (Ln=Pr, Nd or Er) with the potentially tridentate O,N,O chelating ligand 2,6-pyridinedimethanol (H₂pydm) in a 1:2 M ratio were investigated, and complexes with the formula [Ln(H₂pydm)₂(NO₃)₂](NO₃) (Ln=Pr or Nd) (1 and 2) and [Er(H₂pydm)₃](NO₃)₃ (3) were isolated. The compounds contain 10-coordinate Pr(III) and Nd(III) ions that crystallize in the triclinic space group P-1 while the 9-coordinate Er(III) complex crystallizes in the monoclinic system (P2₁/n). A new lanthanide complex, [Pr(H₂pydm)₃](Cl)₃?DMF (4), has been synthesized by reaction of PrCl₃?6H₂O and H₂pydm. The nine-coordinate Pr(III) is bound to three H₂pydm ligands. X-ray crystal structures of 1–4 reveal that the ligand coordinates tridentate via the pyridyl nitrogen and the two hydroxyl oxygens. The electronic absorption spectra of 1–4 show 4f–4f transitions.     

Indium(III)-catalysed aryl sulfonylation reactions

A rapid, high yielding and regioselective process has been developed for the synthesis of biaryl sulfones via sulfonylation reactions catalysed by indium(III) chloride.     

CRYSTAL STRUCTURE OF THE ISOMORPHOUS COMPLEXES TETRAAQUABIS(2,6-DIHYDROXY-BENZOATO-O)(2,6-DIHYDROXY-BENZOATO-O,O)TERBIUM(III) AND HOLMIUM(III) DIHYDRATE

Abstract

The structures of isomorphic Tb(III) and Ho(III) complexes with 2,6-dihydroxybenzoic acid of formula [Tb(C₇H₅O₄] 2H₂O and [Ho(C₇H₅O₄)₃ 4H₂O] 2H₂O has been determined by X-ray diffraction and refined to a residual R = 0.030 for 5376 observed reflections and R = 0.0284 for 5660 observed reflections, for Tb(III) and Ho(III) complexes, respectively. Crystals are triclinic, space group P1 with a= 10.748(2), b=11.309(2), c = 12.452(2)Å, α = 82.28(3), ? = 73.05(5), γ = 68.27(3)° for Tb(III) and a= 10.731(2), b=11.269(2), c = 12.436(2)Å, α = 82.25(3), β = 72.92(3), γ = 68.46(3)° for Ho(III).

In the structure of these monomelic complexes the metal ions are coordinated by oxygen atoms of one bidentate chelating and two monodentate carboxylate groups and four molecules of water. Tb-O distances are in the range 2.323(3)-2.506(3) Å and Ho-0 2.297(3)-2.486(3) Å. The crystal structure, consisting of discrete units of neutral complexes with two molecules of water of crystallization is stabilized by intra-and intermolecular hydrogen bonds.     

Crystal structure of dimethylgold(III) 8-hydroxyquinolinate and 8-mercaptoquinolinate

A crystal-chemical study of dimethylgold(III) complexes with 8-hydroxyquinoline (CH₃)₂Au(OR) and 8-mercaptoquinoline (CH₃)₂Au(SR) (R = C₉H₆N) was performed. Crystal data for (CH₃)₂Au(OR): a = 8.7133(17) Å, b = 27.875(6) Å, c = 8.6688(17) Å, β = 102.76(3)°, Z = 8, ρ(calc) = 2.401 g/cm³, space group P2₁/c, R = 0.0909; for (CH₃)₂Au(SR): a = 3.5401(7) Å, b = 15.689(3) Å, c = 19.910(4) Å, β = 99.81(3)°, Z = 4, ρ(calc) = 2.361 g/cm³, space group P2₁/c, R = 0.0712. Both structures are molecular and involve neutral (CH₃)₂Au(L) molecules, L = C₉H₆NO or C₉H₆NS. In the structures, the molecules are arranged in stacks joined by van der Waals interactions. The average Au…Au intrastack distances are 3.57 Å and 4.34 Å for (CH₃)₂Au(OR) and 3.5 Å for (CH₃)₂Au(SR).     

Crystal structure and luminescence of antimony(III) bromide with aniline

The atomic structure of antimony(III) bromide crystals with anilinium was determined by X-ray diffraction analysis of (C₆H₅NH₃)₂SbBr₅ (a = 19.704(3) Å, b = 7.914(1) Å, c = 25.556(4) Å; space group Pbca, Z = 8, ρ_calc = 2.365 g/cm³). The crystal structure consists of infinite chains of [SbBr₅]^2? complex anions formed by sharing six vertices and the anilinium (C₆H₅NH₃)⁺ cations, through which the chains are linked in layers by N-H...Br hydrogen bonds. The geometrical aspects that determine the luminescent spectral properties of the complex are discussed.     

一类六核三价铁簇化合物的合成及结构表征

选择3种不同尺寸含氮配体（哌嗪、咪唑和三氮唑）与三羟甲基丙烷（H₃tmp）和FeCl₃采用溶剂热反应合成3例六核Fe（Ⅲ）合物：（C₅H₁₄N₂）[Fe₆（μ₆-O）Cl₆（tmp）₄]·2H₂O·CH₃OH （1）、（C₃H₅N₂）₂[Fe₆（μ₆-O）Cl₆（tmp）₄] （2）和（C₄H₈N₃）₃（C₂H₄N₃）[Fe12（μ₆-O）₂Cl₁₂（tmp）₈]·3CH₃OH （3）,并对它们的结构进行表征。发现三元醇配体有利于合成高核金属簇。3个化合物具有相同的阴离子簇[Fe₆（μ₆-O）Cl₆（tmp）₄]^2-。通过晶体学参数,元素分析,红外等手段证实,在化合物1和3的体系中,氮杂环配体经历了N-和C-烷基化反应。     

Hydrothermal Synthesis and Crystal Structure of CaIn2(PO4)2(HPO4): An octahedral-tetrahedral framework ternary calcium indium(III) phosphate

The new ternary calcium indium(III) phosphate CaIn₂(PO₄)₂(HPO₄) with mixed octahedral-tetrahedral framework was synthesized through hydrothermal reaction of stoichiometric amounts of CaO and InCl₃ with excess of H₃PO₄ and H₂O at pH = 1. Single crystal x-ray diffraction studies show the compound to crystallize in monoclinic symmetry, space group P2₁/n (#14) with a = 657.08(6), b = 2023.7(2), c = 665.72(7) pm, β = 91.20(1)°, Z = 4 and R = 0.043. The framework is built up of dimers of edge-sharing InO₆ octahedra forming In₂O₁₀ units sharing all their OXO ligands with PO₄ tetrahedra, and HPO₄ groups.     

Die Kristallstruktur von Tris(N,N-Diethyl-N′ -benzoylthioureato) Rhodium(III)

Crystal Structure of Tris(N,N-Diethyl-N′-benzoylthioureato) Rhodium(III) Rh(C₁₂H₁₅N₂OS)₃ crystallizes in the trigonal space group P-3. The cell parameters are a = 16.660(2), c = 8.479(1) Å and Z = 2. The structure was solved with Patterson and direct methods and refined to a final R-value of 7.05%. Rh^III is octahedrally coordinated to three N,N-Diethyl-N′ -benzoylthiourea molecules, which are bidentately coordinated through their oxygen and sulfur atoms. The Rh? S and Rh? O bond lengths are 2.284 Å and 2.033 Å, respectively.     

Complexes of oxamic acid with Au(III) and Rh(III)

The preparation and some properties of the deprotonated complexes of oxamic acid with Au(III) and Rh(III) are reported. On the basis of analytical results, conductometric measurements, magnetic moments and spectral data (IR and UV-visible), a square planar structure is proposed for K[AuL(OH)₂] and octahedral for K₃[RhL ₃] 3H₂O (whereLH₂=oxamic acid).L ^2– acts as a bidentate, non-bridging ligand.

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Komplexe der Oxamidsäure mit Au(III) und Rh(III)

Zusammenfassung Es wird über die Darstellung und einige Eigenschaften von deprotonierten Komplexen der Oxamidsäure mit Au(III) und Rh(III) berichtet. Auf der Grundlage von analytischen Ergebnissen, Leitfähigkeitsmessungen, magnetischen Momenten und IR- und UV(vis)-spektroskopischen Daten wird für K[AuL(OH)₂] eine quadratisch planare und für K₃[RhL ₃] 3 H₂O eine oktaedrische Struktur vorgeschlagen (LH₂=Oxamidsäure).L ^2– reagiert als zweizähniger, nicht überbrückender Ligand.

     

Crystal structure and luminescence of antimony(III) chloride complex with anilinium chloride

Crystal structure of (C₆H₅NH₃)₃[SbCl₅]Cl·H₂O is determined by X-ray analysis (a = 9.4155(13) Å, b = 11.4344(16) Å, c = 13.1584(18) Å, α = 113.483(2)°, β = 90.383(2)°, γ = 97.323(2)°, space group P \(\bar 1\), Z = 2, ρ_calc = 1.642 g/cm³). The crystal structure is based on [SbCl₅]^2? anions, anilinium cations (C₆H₅NH₃)⁺, isolated Cl^? anions, and water molecules. Structural features responsible for spectral and luminescent properties of the complex are discussed.     

基于双席夫碱配体的两个锰(III)配合物的合成、晶体结构和抑制脲酶活性

制备了一个双席夫碱N,N′-双(3,5-二氟亚水杨基)-1,3-二氨基丙烷(H_2L)。利用H_2L、醋酸锰和硫氰酸铵或者叠氮化钠在甲醇中反应分别制得了配合物[MnL(NCS)(OH_2)](1)和[MnL(μ_(1,3)-N_3)]_n(2)。通过元素分析、红外光谱、核磁共振氢谱对H_2L和其配合物进行了表征,用单晶X射线衍射测定了配合物的结构。席夫碱配体利用其亚胺基氮原子和酚羟基氧原子与Mn进行配位。硫氰酸根配体利用其氮原子配位,而叠氮根配体利用两端的氮原子以桥联的方式进行配位。在每个配合物中,Mn原子都采取八面体配位构型。测试了H_2L和2个配合物对刀豆脲酶的抑制活性。在浓度为100μmol·L~(-1)时,配合物1对脲酶的抑制率为(52.0±3.1)%,其IC50值为(81.0±3.7)μmol·L~(-1),而配合物2却没有活性。还利用分子对接技术研究了配合物1与脲酶的作用方式。     

Das cyclische Thioarsenat(III) (PPh4)2As2S6

The Cyclic Thioarsenate(III) (PPh₄)₂As₂S₆ The reaction of Na₃AsS₄ with tetraphenylphosphonium chloride in ethanol or dimethylformamide proceeds with an intramolecular redox reaction, yielding (PPh₄)₂As₂S₆. According to its X-ray crystal structure analysis (4071 reflections, R = 0.070) the anion consists of a six-membered ring of two As and four S atoms in the chair conformation. The As atoms occupy the ring positions 1 and 3, and each of them has an additional terminal S atom.     

Improved Protocol for Mononitration of Phenols with Bismuth(III) and Iron(III) Nitrates

A simple and efficient multigram procedure was developed for the selective mononitration of various activated phenols. The reaction proceeded smoothly with 0.5 equivalents of Bi(NO₃)₃ · 5H₂O or Fe(NO₃)₃ · 9H₂O in acetone at ambient temperature or at reflux. The desired products were isolated in 62–93% total yield and essentially no overnitrated compounds were detected.     

Das erste Alkali-Erdalkalimetall-Oxo/Peroxo-Aurat(III): NaBa4AuO4(O2)2

On the first Alkaline-Alkaline-Earth-Oxo/Peroxo-Aurate(III): NaBa₄AuO₄(O₂)₂ The hitherto unknown compound NaBa₄AuO₄(O₂)₂ was prepared by oxidizing of barium gold alloy with Na₂O₂ in closed Ag-bombs. X-ray single crystal investigation led to tetragonal symmetry space group DI4/mmm, a = 5.939; c = 15.393 Å, Z = 2. NaBa₄AuO₄(O₂)₂ shows a distorted square antiprismatic surrounding of Ba²⁺ by four peroxo groups on one side and four O^2? on the opposite. Au³⁺ shows the usual square planar polygons of AuO₄. Na⁺ is coordinated by four O^2? ions in the base of an octahedron and two peroxo groups in the apical positions.     

Thermogravimetric and spectroscopic studies on La(III) and Ce(III) complexes with some thio-schiff bases

Solid complexes of five derivatives of thio-Schiff bases with La(III) and Ce(III) ions were prepared and characterized by elemental and thermogravimetric analyses. The suggested general formula of the solid complexes is [ML₂(H₂O)X]·2H₂O, whereM=trivalent lanthanide ion,L=Schiff base andX=Cl^? or ClO ₄ ^? . Information about the water of hydration, the coordinated water molecules, the coordination chemistry and the thermal stability of these complexes was obtained and is discussed. Additionally, a general scheme of thermal decomposition of the lanthanide-Schiff base complexes is proposed.