Reactions of tetrachlorodioxouranate(VI) ion with neutral and protic ligands

Summary The reactions of [bipyH₂][UO₂Cl₄]·3H₂O (bipyH₂=diprotonated 2,2-bipyridyl) with a series of neutral and protic oxygen donor ligands have been investigated. N,N-dimethyl formamide (DMF), N,N-dimethyl acetamide (DMA) and dimethyl sulphoxide (DMSO) gave compounds of the type [bipyH₂][UO₂Cl₄(L)₂] (L=DMF or DMA) and [bipyH₂][UO₂Cl₄(DMSO)_n] (DMSO)_3-n (n=1 or 2), while [bipyH₂][UO₂Cl₄-(3PNO)(DMSO)_n](DMSO)_2-n (n=1 or 2) and [bipyH][UO₂Cl₃(4PNO)(DMSO)] were obtained with 3-picoline N-oxide (3PNO) and 4-picoline N-oxide (4PNO) respectively from DMSO medium. With excess 2-picoline N-oxide (2PNO) the compound [bipyH][UO₂Cl₃(2PNO)](DMSO) was obtained. Reaction with acetyl acetone (AcAcH) and 8-hydroxy quinoline (QH) in 1:1 mole ratio in DMSO gave compounds of the type [bipyH₂][UO₂Cl₃(L)(DMSO)] (L=AcAc or Q). The compounds have been investigated by i.r. spectra, powder x-ray diffraction and molar conductivity measurements.     

Oxidation of secondary alcohols byN-methylmorpholine-N-oxide (NMO) catalyzed by Ru(II) halosulfoxide complexes. A kinetic study

RuX₂(DMSO)₄ (X=Cl,cis; Br,trans) undergoes ligand substitution in N,N-dimethylformamide (DMF) to give RuX₂(DMSO)₃DMF, which catalyzes the oxidation of secondary alcohols by NMO to ketones. Kinetics of the reaction catalyzed bytrans-RuBr₂(DMSO)₄ differed from that ofcis-RuCl₂(DMSO)₄. A mechanism is proposed involving the formation of Ru(IV)oxo species as the active intermediate and a rate expression is derived.     

Mixed Halide Tin(IV) Complexes with NN-dimethylformamide and dimethylsulfoxide

By oxidative-addition reactions of Br₂ and I₂ to SnCl₂ in the presence of NN-dimethylformamide (DMF) and dimethylsulphoxide (DMSO), the mixed halide complexes SnCl₂Br₂L₂ (L ? DMF, DMSO) and SnCl₂I₂(DMSO)₂ are obtained. The IR, Raman and ¹¹⁹Sn Mössbauer spectra suggest that the ligands coordinate in cis position through the oxygen atom, a C₁ symmetry being found for SnCl₂I₂(DMSO)₂. SnCl₂Br₂(DMSO)₂ crystallizes in the triclinic space group P1 with two molecules per unit cell. The lattice constants are a = 752.4, b = 1350.6, c = 820.3 pm, α = 89.60, β = 117.31 and γ = 90.83°. 2317 independent observed reflexions were used for refinement: R = 8.4%. The structure is disordered and our results are again consistent with a C₁ molecular symmetry. Mixtures of products were obtained by reaction of SnCl₂ with I₂ in the presence of DMF and by reaction of SnBr₂ with I₂ in the presence of DMSO.     

Solid-State Structures and Photoluminescence of Lamellar Architectures of Cu(I) and Ag(I) Paddlewheel Clusters with Hydrogen-Bonded Polar Guests

Two hexanuclear paddlewheel-like clusters appending six carboxylic-acid pendants have been isolated with the inclusion of polar solvent guests: [Cu₆(Hmna)₆]·7DMF (1·7DMF) and [Ag₆(Hmna)₆]·8DMSO (2·8DMSO), where H₂mna = 2-mercaptonicotininc acid, DMF = N,N’-dimethylformamide, and DMSO = dimethyl sulfoxide. The solvated clusters, together with their fully desolvated forms 1 and 2, have been characterized by FTIR, UV–Vis diffuse reflectance spectroscopy, TG-DTA analysis, and DFT calculations. Crystal structures of two solvated clusters 1·7DMF and 2·8DMSO have been unambiguously determined by single-crystal X-ray diffraction analysis. Six carboxylic groups appended on the clusters trap solvent guests, DMF or DMSO, through H-bonds. As a result, alternately stacked lamellar architectures comprising of a paddlewheel cluster layer and H-bonded solvent layer are formed. Upon UV illumination (λ_ex = 365 nm), the solvated hexasilver(I) cluster 2·8DMSO gives intense greenish-yellow photoluminescence in the solid state (λ_PL = 545 nm, Φ_PL = 0.17 at 298 K), whereas the solvated hexacopper(I) cluster 1·7DMF displays PL in the near-IR region (λ_PL = 765 nm, Φ_PL = 0.38 at 298 K). Upon complete desolvation, a substantial bleach in the PL intensity (Φ_PL < 0.01) is observed. The desorption–sorption response was studied by the solid-state PL spectroscopy. Non-covalent interactions in the crystal including intermolecular H-bonds, CH⋯π interactions, and π⋯π stack were found to play decisive roles in the creation of the lamellar architectures, small-molecule trap-and-release behavior, and guest-induced luminescence enhancement.     

Synthese und Kristallstruktur von [Ba(18-Krone-6)(DMF)4][Cd(Se4)2]

Synthesis and Crystal Structure of [Ba(18-Crown-6)(DMF)₄][Cd(Se₄)₂] The title compound has been prepared by the reaction of a DMF-solution of lithium polyselenide with BaSe₂ and cadmium acetate in the presence of 18-crown-6, forming black crystals. The compound was characterized by IR spectroscopy and by an X-ray structure determination. Space group P2/a, Z = 4, 5392 observed unique reflections, R = 0.048. Lattice dimensions at ?90°C: a = 2021.9(12); b = 1019.8(6); c= 2270.8(14)pm, ß = 106.98(4)°. The structure consists of [Ba(18-crown-6)(DMF)₄]²⁺ ions, in which the barium ions are coordinated by the six oxygen atoms of the crown ether molecule and by four oxygen atoms of the DMF molecules, and of [Cd(Se₄)₂]^2? ions. The cadmium atoms are coordinated by two tetraselenide ions in a chelating fashion.     

Dioxomolybdenum(VI) complexes of 2-hydroxybenzaldehyde 4-phenyl-S-methylthiosemicarbazone

Mixed ligand complexes of dioxomolybdenum(VI) with 2-hydroxybenzaldehyde 4-phenyl-S-methylthiosemicarbazone (H₂L) were prepared with the formula [MoO₂(L)D] (D = H₂O, methyl, n-butyl, and n-undecyl alcohol, DMF, DMSO, pyridine, 4-picoline, and 3,5-lutidine). The compounds were characterized by elemental analysis, IR and ¹H NMR spectroscopy. The thermal decomposition of the compounds were investigated by using TGA, DTG, and DTA methods in air, and the thermal behavior depending on the second ligand molecule was discussed. A single crystal of the DMF coordinated complex was studied by X-ray diffractometry. The text was submitted by the authors in English.     

Crystal Structures,Spectroscopic and Magnetic Behaviour of Dimeric Copper(II) 2‐Methylthionicotinate Adducts with Dimethylformamide and Dimethylsulfoxide

The structural, spectroscopic and magnetic properties of two dimeric complexes, [Cu₂(2‐MeSnic)₄(DMSO)₂] ( I ) and [Cu₂(2‐MeSnic)₄(DMF)₂] ( II ) (where 2‐MeSnic = 2‐methylthionicotinate, DMF = dimethylformamide and DMSO = dimethylsulfoxide), are reported. The characterization is based on elemental analysis, infrared, electronic and EPR spectra, and magnetic susceptibility measurements over a temperature range of 1.9 — 300 K. Both complexes adopt dimeric paddle‐wheel cage structures as revealed by X‐ray structure analysis. The dimeric molecule of I is centrosymmetric and centred at the inversion center of the space group P 2₁/c (Z = 2), while the structure of II contains a crystallographically independent molecule IIa , and a centrosymmetrical molecule IIb which is centred at the inversion centre of the space group P 2₁/n (Z = 6).     

Effects of Coordinating Solvents on the Supramolecular Assembling of Tectons arised from the Metallation of Sulfamethoxazole: Synthesis and Structural Characterization of Polymeric [Cd(sulfamethoxazolato)2(L)2]n {L = N,N‐dimethylformamide (DMF); Dimethyl Sulfoxide (DMSO)} and [Cd(sulfamethoxazolato)2(Py)2]n·n(Py)(Py =pyridine)

Cadmium acetate reacts with sulfamethoxazole (5‐methyl‐3‐isoxazolyl sulfanilamide) and with DMF / DMSO / pyridine to give the crystalline polymers [Cd(sulfamethoxazolato)₂(L₂)]_n {L = DMF ( 1 ), DMSO ( 2 )} and [Cd(sulfamethoxazolato)₂(Py)₂]_n·n(Py) ( 3 ). Complexes 1 , 2 and 3 confirm the tectonic character of the [Cd(sulfamethoxazolato)₂(L)₂] moieties and the remarkable ability of the {Cd(sulfamethoxazolato)₄} fragments to be non selectively stabilized by monodentate ligands. In the polymeric assemblies of the title complexes the cadmium(II) atoms are linked through sulfamethoxazolato anions which alternate in their coordination with the isoxazolic N‐atoms and the aromatic amino groups. The chains of vicinal rings build tunnels along the crystallographic c axis.     

Isotope effects on thermodynamic properties in four binary systems: Water (or heavy water) + dimethylsulfoxide (or N,N-Dimethylformamide) at 25‡C

Excess enthalpy, excess isobaric heat capacity, density, and speed of sound in mixtures of heavy water (D₂O) + dimethylsulfoxide (DMSO), and D₂O + dimethylformamide (DMF) were measured at 25‡C. The same properties of the mixtures of normal water + DMSO, and H₂O + DMF were also measured to estimate isotope effects on the thermodynamic excess functions. Both DMSO and DMF are proton acceptors and thus form hydrogen bonds with water. Large negative excess enthalpies and volumes of mixing and excess isentropic compressibilities show that the hydrogen bonding structures of DMSO and DMF with water are stronger and more compact than those in pure water. The excess heat capacity of DMSO-containing mixtures changes sign from negative to positive with increasing water content. The deviations of the excess properties of D₂O systems from those of H₂O systems indicate that the hydrogen bonding structure with D₂O is stronger and more compact.     

Die Kristallstrukturen der Polytelluride [Ca(DMF)6]Te4, [Sr(15-Krone-5)2]Te4 · H2O, {[BaCl(18-Krone-6)(DMF)2]2[BaCl(18-Krone-6)(DMF) (H2O)]2(Te4)2} und [Ph3PNPPh3]2Te5 · 2 DMF

Crystal Structures of the Polytellurides [Ca(DMF)₆]Te₄, [Sr(15-Crown-5)₂]Te₄ · H₂O, {[BaCl(18-Crown-6)(DMF)₂]₂[BaCl(18-Crown-6)(DMF) (H₂O)]₂(Te₄)₂}, and [Ph₃PNPPh₃]₂Te₅ · 2 DMF The title compounds were formed by alkalimetal polytelluride solutions in dimethylformamide (DMF) in the presence of the corresponding counter ions as well as in the presence of 15-crown-5 or 18-crown-6. Single crystals were obtained upon using additional diethylether. [Ca(DMF)₆]Te₄: Space group C2/c, Z = 4, 1024 observed unique reflections, R = 0.055. Lattice dimensions at ?70°C: a = 1776.1; b = 813.0 c = 2545.9pm; β = 102.90°. The compound consists of centrosymmetric [Ca(DMF)⁶]²⁺ ions, in which the calcium ions are octahedrally coordinated by the six oxygen atoms of the DMF molecules, and chain-like Te [Sr)15-crown-5)₂]Te₄ · H₂O: Space group C2/c, Z = 4, 3322 observed unique reflections, R = 0.058. Lattice dimensions at ?70°C: a = 1450.5; b = 1407.3; c = 1660.9 pm; β = 110.22°. The compounds forms centrosymmetric cations [Sr(15-crown-5) ₂]²⁺, in which the Sr²⁺ ion is sandwich-like surrounded by the ten oxygen atoms of the crown ether molecules, and chain-like Te₄^2? ions, which are associated in the lattice forming polymeric chains. {[BaCl(18-crown-6)(DMF) ₂]₂[BaCl(18-crown-6)(DMF)· (H₂O)] ₂(Te₄)₂}: Space group P1 , Z = 1, 3189 observed unique reflections, R = 0.054. Lattice dimensions at 19°C: a = 986.1; b = 1052.8; c = 2696.4 pm; α = 89.34°; β = 88.68°; γ = 89.56°. The compound consists of chain-like Te ions without symmetry and of the two somewhat different cations [BaCl(18-crown-6)(DMF) ₂]₂²⁺, in which the Ba²⁺ ions dimerize via centroysmmetric rings. Along with the six oxygen atoms of the crown ether molecules and the oxygen atoms of the DMF molecules, the oxygen atoms of the DMF and water molecule, respectively, the Ba⁺ ions achieve coordination number ten. [Ph₃PNPPh₃]₂Te₅ · 2DMF: Space group Pc, Z = 2, 5971 observed unique reflections, R = 0.058. Lattice dimensions at 20°C: a = 20°C: a = 1085.2; b = 1287.0; c = 2715.9 pm; β = 90.19°. The compounds consists of [Ph₃PNPPh₃]₊ ions, chain-like Te₅^2? ions, and incorporate DME molecules without bonding interaction. The ₅^2? ions are associate via polymeric chains in which left- and right handed individuals are alternating.     

[Na(12-Krone-4)2]2[Ni(Se4)2] · DMF; Synthese,Kristallstruktur und magnetisches Verhalten

[Na(12-Crown-4)₂]₂[Ni(Se₄)₂] · DMF; Synthesis, Crystal Structure, and Magnetic Behaviour The title compound has been prepared from NiCl₂ and sodium polyselenide in dimethylformamide solution in the presence of 12-crown-4, forming black crystal needles. They were characterized by an X-ray structure determination, by FIR spectroscopy as well as by the magnetic behaviour. [Na(12-crown-4)₂]₂[Ni(Se₄)₂] · DMF crystallizes monoclinically in the space group P2₁, 3650 observed unique reflections, R = 0.046. Lattice dimensions at ?80°C: a = 1020.3(2); b = 1889.5(2); c = 1498.7(3) pm; β = 108.29(1)°. The compound has an ionic structure, in which the sodium atoms of the [Na(12-crown-4)₂]⁺ cations are coordinated by the oxygen atoms of the crown ether molecules in an antiprismatic fashion. The nickel atom of the anion [Ni(Se₄)₂]^2? is surrounded by four selenium atoms of the tetraselenide chelates in an almost planar environment. The DMF molecules are inserted in the lattice without a bonding interaction. The magnetic susceptibility observed in the temperature interval 4.2 to 330K can be interpreted by means of a ³E ground term and D₂ as local symmetry, which was established by X-ray crystallography.     

Der erste sechsgliedrige Zinn(II)-Übergangsmetallzyklus – [Mn(CO)4SnCl(DMF)]3

First Compound with a Six-Membered Tin(II) Transition Metal Ring – [Mn(CO)₄SnCl(DMF)]₃ Tin(II) chloride and dimanganese decacarbonyl were reacted in dimethyl-(DMF) at 150°C or monomethylformamide (MMF) at 120°C to yellow product solvates of the type [Mn(CO)₄SnCl(D)]₃ (D = DMF and MMF). Their identification in the case of the compound [Mn(CO)₄SnCl(DMF)]₃ was undertaken by a single crystal X-ray analysis. As result of this determination, its central molecular fragment contained a non-planar (SnMn)₃ ring with the following average bond parameters: Sn? Mn bond lengths of 258.8(5) pm, endocyclic bond angle at Mn Atom of 90.5(2)° and the corresponding angle at Sn atom of 141.6(2)°. After the result of ¹¹⁹Sn Mößbauer spectroscopic measurements of the title substance a tin(II) oxidation state was present. The ν(CO) i.r. absorption bands and ¹H n.m.r. data of both obtained products were measured for a further characterization. With view to the mechanistic pathway of the product formation, it was ascertained by separate experiments that the postulated intermediate Cl₃SnMn(CO)₅ and tin(II) chloride in DMF solution produced the title compound.     

Zinc(II)–Organic Framework Films with Thermochromic and Solvatochromic Applications

Multiple-stimuli-responsive photoluminescence films based on a Zn^II–organic framework, {[Zn₂(Htpim)(3,4-pydc)₂] ⋅ 4 DMF ⋅ 4 H₂O}_n ( 1 , Htpim=2,4,5-tri(4-pyridyl)imidazole, 3,4-H₂pydc=3,4-pyridinedicarboxylic acid), were fabricated. This compound consisted of a 2D corrugated layer, {Zn(3,4-pydc)}_n, which was further pillared using a Y-shaped pillar N-donor ligand (Htpim) to form a 3D-pillared-layer framework with 1D open channels. The rectangular channels in the as-synthesized compound are fully occupied by guest DMF and H₂O molecules. The framework exhibits instant and reversible thermochromic properties corresponding to the removal of different H₂O and DMF guest molecules as temperature increases. The pale-yellow crystal undergoes significant redshifting to a greenish emission centered at 530 nm. Compound 1 also showed remarkable solvatochromic effects in the presence of various organic solvents without affecting its structural integrity. In addition, polycrystalline MOF films were grown on an α-Al₂O₃ support for switchable and fast-response thermochromic and solvatochromic sensors.     

Volumes of Activation for Dimethylsulfoxide and N,N-Dimethylformamide Exchange with Hexasolvates of Aluminium (III) and Gallium (III) Ions in Deuterionitromethane Solution

High-pressure ¹H-NMR. has been used to determine volumes of activation (ΔV#) for solvent exchange with [M(S)₆]³⁺ ion (M = Al(III), Ga(III); S = dimethylsulfoxide (DMSO) and N,N-dimethylformamide (DMF)) in [²H]₃-nitromethane solution. For Al(III),Δ V# = + 15.6 ± 1.4 (S = DMSO, 358.5 K) and ΔV# = + 13.7 ± 1.2 cm³mol^?1 (S = DMF, 354.5 K), whilst for Ga(III), ΔV# = + 13.1 ± 1.0 (S = DMSO, 334.6 K) and ΔV# = +7.9 ± 1.6 cm³mol^?1 (S= DMF, 313.8 K). Variable temperature studies over a temperature range of 107.2 K (Al(III)) and 101.1 K (Ga(III)) were carried out for solvent exchange with [M(DMF)₆]³⁺ ions in [²H]₃-nitromethane solution, using stopped-flow NMR, and conventional linebroadening, and gave ΔH# = 88.3 ± 0.9 and 85.1 ± 0.6 kJ+ mol^?1, and ΔS# = 28.4 ± 2.7 and 45.1 ± 1.9 JK^?1 mol^?1 for Al(III) and Ga(III) ions respectively. All of these results are consistent with dissociative modes of activation.     

Synthese und Kristallstruktur von [Na(12-Krone-4)2]2[Hg(Se4)2] · 1,5 DMF

Synthesis and Crystal Structure of [Na(12-Crown-4)₂]₂[Hg(Se₄)₂] · 1.5 DMF . The title compound has been prepared by the reaction of Na₂Se₄ with mercury acetate in DMF solution in the presence of 15-crown-5, forming dark red crystal needles. [Na(12-crown-4)₂]₂[Hg(Se₄)₂] · 1.5 DMF crystallizes in the space group C2/c with eight formula units per unit cell. The structure was determined with 3 824 observed unique reflections, R = 0.085. Lattice dimensions at - 70°C: a = 2 884(2), b = 1 407.7(7), c = 2 843(2) pm, β = 93.93(5)°. The structure consists of [Na(12-crown-4)₂]⁺ ions with a sandwichlike coordination of the crown ether molecules, and of [Hg(Se₄)₂]^2? ions, in which the mercury atom is coordinated by two tetraselenido ions in a chelating fashion. The [Hg(Se₄)₂]^2? ions are arranged to infinite chains via Se…?Se contacts.     

A Novel Keggin Units-Supported Complex: Synthesis,Characterization and Crystal Structure of [(CH3)2NH2]6[Cu(DMF)4(GeW12O40)2] · 2DMF

A novel hybrid compound, [(CH₃)₂NH₂]₆[Cu(DMF)₄(GeW₁₂O₄₀ ^4-)₂] [sdot] 2DMF, has been synthesized from H₄GeW₁₂O₄₀ [sdot] n H₂O, CuCl₂ and N, N -dimethylformamide (DMF) in aqueous solution and characterized by elemental analysis, UV and IR spectra. Single crystal X-ray structure analysis shows that the crystal consists of a α-Keggin heteropolyanion-supported anion [Cu(DMF)₄(GeW₁₂O₄₀ ^4-)₂], two free N, N-dimethylformamide molecules, six protonated dimethylamine (DMA) molecules, and that the coordinating atoms of DMF are the oxygen atoms of C=O group. Thermal analysis indicates that the thermal stability of the GeW₁₂O₄₀ ^4- anion in the title compound is stronger than that in acid.     

Chemical Conversion of Hg‐Clusters: Synthesis and Crystal Structure of $ {\rm [(DMSO)_2 Co(NC \overline{S)_4(Hg}-TePh)_2]_{\rm n} }$, the First Compound Containing a Polymeric Hg—Te Chain

The six‐membered ring Hg₃Te₃ of [Hg₃Cl₃(μ‐TePh)₃]·2 DMSO {(Ph = C₆H₅; DMSO = (CH₃)₂SO} was opened by redissolution with DMSO, reacting with Co[Hg(SCN)₄] and affording polymeric . The monoclinic novel compound belong to the space group P2₁/n and assembles in a bidimensional lattice tetrahedral Hg^II(SCN)₂Te₂‐ and octahedral Co^II(NCS)₄(DMSO)₂‐chains linked trough SCN bridges along the crystallographic axis b and diagonally to the ac axes. The structure of [(DMSO)₂Co(NCS)₄(Hg—TePh)₂]_n is limited by the DMSO ligands in the axial positions of the Co‐octahedrons.     

Solvent Molecule Controlled Zinc(II) Metal‐Organic Frameworks with Different Topology

Two zinc(II) coordination polymers, namely [Zn₂(bptc)(DMF)₂(H₂O)]_n ( 1 ) and [Zn(bptc)_0.5(DMA)]_n ( 2 ) (H₄bptc = biphenyl‐3,3′,5,5′‐tetracarboxylic acid, DMF = N,N′‐dimethylformamide, DMA = N,N′‐dimethylacetamide), were obtained under solvothermal conditions by varying the reaction solvents. Single crystal X‐ray diffraction analyses revealed that compound 1 features a 3D PtS type framework based on dinuclear [Zn₂O(COO)₂] subunits and compound 2 features a 3D lvt type framework based on paddle‐wheel shaped [Zn₂(COO)₄] subunits. Moreover, the luminescent and thermal stabilities of these two compounds were investigated.     

Synthesis and Characterization of Two Trinuclear Nickel(II) Complexes

Two novel trinuclear nickel(II) complexes have been synthesized and characterized by X‐ray single crystal diffraction. Compound [Ni₃(ashz)₃(py)₂(DMF)₂]·(DMF)₂ ( 1 ) crystallizes in the monoclinic, space group C2/c, with a = 22.114(2), b = 10.509(9), c = 19.485(2) Å, β = 114.443(1)°, Z = 4; compound [Ni₃(acshz)₃(py)₂(DMF)₂]·(DMF)₂ ( 2 ) crystallizes in the monoclinic space group P2₁/n with a = 20.0620(2), b = 9.7017(6), c = 25.0533(2) Å, β = 97.0610(2)°, Z = 4, where ashz and acshz are deprotonated N‐acetylsalicylhydrazide (H₃ashz) and N‐acetyl‐5‐chlorosalicylhydrazide (H₃acshz), respectively. The crystal structure analysis of 1 and 2 showed that three Ni²⁺ ions in a linear arrangement are bridged by two ligands ((ashz)^3? or (acshz)^3?) to form a neutral nuclear with two four‐coordinate square‐planar nickel ions linked by a six‐coordinate octahedral central nickel ion.     

三维开放骨架镧系金属有机配位聚合物Tm(BTC)(DMF)(DMSO)的合成、结构和性质

以稀土元素铥(Tm) 作为金属中心, 均苯三甲酸(H3BTC)作为有机配体制备了一个新型的三维配位聚合物 Tm(BTC)(DMF)(DMSO), 并通过X射线单晶衍射、元素分析、热重分析、吸附测试等手段对其进行了表征.