Crystal structure and electrical properties of the mixed valent titanium oxysulfide Sm2Ti2S2O4.5

A new phase Sm₂Ti₂S₂O_4.5 was synthesized and its crystal structure was solved by single-crystal X-ray diffraction. This compound crystallizes in the monoclinic system (C2/m) with lattice constants a=17.9987(11) Å, b=3.71607(14) Å, c=12.6172(8) Å and β=133.645(4)°. The structure is built up from double chains of Ti-centered octahedra between which Sm-polyhedra develop. In spite of very close formulations, the structure of Sm₂Ti₂S₂O_4.5 differs completely from that of the defect Ruddelsden-Popper phase Sm₂Ti₂S₂O₅ previously reported. The title compound presents a mixed valence for titanium with Ti(III) (d¹) and Ti(IV) (d⁰) located in different crystallographic sites. However, conductivity measurements show that this compound is non-metallic.     

Synthesis of a ferrocenyl uracil PNA monomer for insertion into PNA sequences

The deprotection of the tert-butyl group of a ferrocenyl uracil Peptide Nucleic Acid (PNA) monomer, Fmoc-aeg(R)-O^tBu (1) was achieved using a two step synthesis involving hydrolysis in basic conditions to give first the zwitterion of ⁺NH₃-aeg(R)-O⁻ (7). Compound 7 was reacted in situ with N-(9-fluorenylmethoxycarbonyloxy)succinimide to obtain the expected compound Fmoc-aeg(R)-OH (2) (Abbreviations: Aeg = (2-aminoethyl)-glycine; Fmoc = 9-fluorenylmethoxycarbonyl; O^tBu = tert-butyl; R = 5-(N-ferroce-nylmethylbenzamido)uracyl).     

Aerobic oxidation of 1,3,5-triisopropylbenzene using N-hydroxyphthalimide (NHPI) as key catalyst

The first systematic study on the aerobic oxidation of 1,3,5-triisopropylbenzene was examined by the use of N-hydroxyphthalimide (NHPI) as a key catalyst. It was found that 1,3,5-triisopropylbenzene was efficiently oxidized with O₂ in the presence of a catalytic amount of NHPI and azobisisobutyronitrile (AIBN) at 75 °C. Upon treatment of the resulting products with sulfuric acid followed by acetic anhydride led to 5-acetoxy-1,3-diisopropylbenzene and 3,5-diacetoxy-1-isopropylbenzene as major products and a small amount of 1,3,5-triacetoxybenzene. When t-butylperoxypivalate (BPP) was employed as a radical initiator, the oxidation could be achieved in good yield even at 50 °C. This oxidation provides a facile method for preparing phenol derivatives bearing an isopropyl moiety, which can be used as pharmaceutical starting materials.     

A portable and low cost equipment for flow injection chemiluminescence measurements

A compact, reliable and low cost flow injection chemiluminescence system is described. The flow system consists of a set of solenoid micro-pumps that can dispense reproductive micro-volumes of solutions. The luminometer was based on a coiled cell constructed from polyethylene tubing that was sandwiched between two large area photodiodes. The whole equipment costs about US$ 750 and weights ca. 3 kg. Equipment performance was evaluated by measuring low concentrations of hydrogen peroxide by oxidation of luminol and for the determination of ammonium, based on its inhibition of the luminescence provided by the reaction of luminol and sodium hypochlorite. Linear responses were achieved within 1.0-80 μmol L⁻¹ H₂O₂ and 0.6-60 μmol L⁻¹ NH₄⁺ with detection limits estimated as 400 nmol L⁻¹ H₂O₂ and 60 nmol L⁻¹ NH₄⁺ at the 99.7% confidence level. Coefficients of variation were 1.0 and 1.8%, estimated for 20 μmol L⁻¹ H₂O₂ and 15 μmol L⁻¹ NH₄⁺ (n = 20), respectively. Reagent consumption of 55 μg luminol, effluent volume of 950 μL per determination and sampling rate of 120 samples per hour were also achieved.     

Preparation, crystal structure, and superconductive characteristics of new oxynitrides (Nb1−xMx)(N1−yOy) where M=Mg, Si, and x≈y

New niobium oxynitrides containing either magnesium or silicon were prepared at 1000 °C by ammonia nitridation of oxide precursors obtained via the citrate route. The products had rock-salt type crystal structures. Crystallinity was improved by annealing in 0.5 MPa N₂ and the final compositions were (Nb_0.95Mg_0.05)(N_0.92O_0.08) at 1500 °C and (Nb_0.87Si_0.09□_0.04)(N_0.87O_0.13) at 1200 °C. The magnesium and oxide ions partially co-substitute the niobium and nitride ions in the octahedral sites of the δ-NbN lattice, respectively. Silicon ions were also successfully doped together with oxide ions into the rock-salt type NbN lattice. The Si doped product exhibited relatively large displacement at the octahedral sites and was accompanied by a small amount of cation vacancies. Superconductivity was improved by annealing to obtain critical temperatures/volume fractions of T_c=17.6 K/100% for Mg- and T_c=16.2 K/95% for the Si-doped niobium oxynitrides.     

The formation and physicochemical characterization of Al2O3-doped manganese ferrites

Mn/Fe mixed oxide solids doped with Al₂O₃ (0.32-1.27 wt.%) were prepared by impregnation of manganese nitrate with finely powdered ferric oxide, then treated with different amounts of aluminum nitrate. The obtained samples were calcined in air at 700-1000 °C for 6 h. The specific surface area (S_BET) and the catalytic activity of pure and doped precalcined at 700-1000 °C have been measured by using N₂ adsorption isotherms and CO oxidation by O₂. The structure and the phase changes were characterized by DTA and XRD techniques. The obtained results revealed that Mn₂O₃ interacted readily with Fe₂O₃ to produce well-crystallized manganese ferrite (MnFe₂O₄) at temperatures of 800 °C and above. The degree of propagation of this reaction increased by Al₂O₃-doping and also by increasing the heating temperature. The treatment with 1.27 wt.% Al₂O₃ followed by heating at 1000 °C resulted in complete conversion of Mn/Fe oxides into the corresponding ferrite phase. The catalytic activity and S_BET of pure and doped solids were found to decrease, by increasing both the calcination temperature and the amount of Al₂O₃ added, due to the enhanced formation of MnFe₂O₄ phase which is less reactive than the free oxides (Mn₂O₃ and Fe₂O₃). The activation energy of formation (ΔE) of MnFe₂O₄ was determined for pure and doped solids. The promotion effect of aluminum in formation of MnFe₂O₄ was attributed to an effective increase in the mobility of reacting cations.     

Flow-injection methylene blue-based spectrophotometric method for the determination of peroxide values in edible oils

A flow-injection method for measuring the peroxide value (PV, mequiv. O₂ kg⁻¹) in edible oils is described. The technique is based on spectrophotometric monitoring at 660 nm of methylene blue (MB), generated from leucomethylene blue (LMB) oxidation with peroxides present in oil samples. After being optimized, the method was validated in terms of linearity, precision sensitivity and recovery.Linear calibration graph was obtained in the range 0.1-5 mequiv. O₂ kg⁻¹, with a detection limit (S/N  =  3) of 0.014 mequiv. O₂ kg⁻¹. The precision of the method (R.S.D., n = 9) for within and between-days is better than 1.5% and 2.2%, respectively at 0.4 mequiv. O₂ kg⁻¹. The method was applied successfully to the determination of PV in six edible oil samples, and compared to the classical official method. Using the linear regression test, Student's t-test and variance ratio F-test, there was no significant difference between the compared methods. The proposed method is accurate, simple, cheap and could be used to control edible oil rancidity with a high sample throughputs (30 samples h⁻¹).     

Hydrothermal synthesis and characteristics of 3-D hydrated bismuth oxalate coordination polymers with open-channel structure

Two new 3-D porous bismuth coordination polymers, (C₅NH₆)₂[Bi₂(H₂O)₂(C₂O₄)₄]·2H₂O 1 and (NH₄)[Bi(C₂O₄)₂]·3H₂O 2, have been hydrothermally synthesized and characterized by single-crystal X-ray diffraction. Compound 1 crystallizes in the monoclinic symmetry, P2₁/c space group with a=10.378(2) Å, b=17.285(3) Å, c=16.563(5) Å, α=90°, β=119.66(2)°, γ=90°, V=2581.8(10) Å³, Z=4, R₁=0.0355 and wR₂=0.0658 for unique 4713 reflections I >2σ(I). Compound 2 crystallizes in the tetragonal symmetry, I4₁/amd space group with a=11.7026(17) Å, b=11.7026(17) Å, c=9.2233(18) Å, α=90°, β=90°, γ=90°, V=1263.1(4) Å³, Z=32, R₁=0.0208 and wR₂=0.0518 for unique 359 reflections I> 2σ(I). Compounds 1 and 2 are 3-D open-framework structures with a 6⁶ uniform net, which consist of honeycomb-like layers connected to each other by oxalate units. While different guest molecules fill in their cavities of honeycomb-like layers, study of ultrasonic treatment on 2 indicates the replacement of NH₄⁺ by K⁺ on potassium ion exchange. Thermogravimetric analysis indicates that the open-channel frameworks are thermally stable up to 200 °C, and other characterizations are also described by elemental analysis, IR and ultraviolet-visible diffuse reflectionintegral spectrum (UV-Vis DRIS).     

New indium selenite-oxalate and indium oxalate with two- and three-dimensional structures

Two new indium(III) compounds with extended structures, [In₂(SeO₃)₂(C₂O₄)(H₂O)₂]·2H₂O (I) and [NH₃(CH₂)₂NH₃][In(C₂O₄)₂]₂·5H₂O (II), have been prepared under mild hydrothermal conditions and structurally characterized by single-crystal X-ray diffraction, thermogravimetric analysis and infrared spectroscopy. Compound I crystallizes in the triclinic system, space group P-1, with a=5.2596(11) Å, b=6.8649(14) Å, c=9.3289(19) Å, α=101.78(3)°, β=102.03(3)°, γ=104.52(3)°, while compound II crystallizes in the orthorhombic system, space group Fdd2, with a=15.856(3) Å, b=31.183(6) Å, c=8.6688(17) Å. In compound I, indium-selenite chains are bridged by oxalate units to form two-dimensional (2D) In₂(SeO₃)₂C₂O₄ layers, separated by non-coordinating water molecules. In compound II, the indium atoms are connected through the oxalate units to generate a 3D open framework containing cross-linked 12- and 8-membered channels.     

Syntheses and structures of zinc and tin(II) compounds with hemilabile N-silyl-tert-butylamido and N-silyl-p-tolylamido ligands that contain pendent tert-butoxy groups

Syntheses and solid-state structures of zinc and tin(II) compounds, containing the N-silyl-amide ligands (O^tBu)(NR)SiMe₂, R = ^tBu (L^tBu), or R = p-tolyl (L^pTol), are reported. The N-silyl amines were synthesized by modified published procedures from commercially available Me₂SiCl₂, ^tBuOH, and ^tBuNH₂, or p-Me-C₆H₄NH₂, respectively. Treatment of SnCl₂ with LiL^pTol furnished Sn(L^pTol)₂, which was X-ray structurally characterized and shown to contain two covalent Sn-N bonds and two asymmetrical O → Sn donor bonds. The single-crystal X-ray structure of Sn(L^tBu)₂ revealed a much more symmetrically-coordinated, pseudo-trigonal-bipyramidal tin atom. Aminolysis of diethylzinc with HL^pTol produced [EtZn(L^pTol)]₂, which crystallized as a centrosymmetric dimer, containing four-coordinate zinc atoms connected by bridging amides. Zinc dichloride, by contrast, reacted with two equivalents of LiL^tBu to produce the homoleptic, pseudo-spirocyclic Zn(L^tBu)₂.     

A rare multi-coordinate tellurite, NH4ATe4O9·2H2O (ARb or Cs): The occurrence of TeO3, TeO4, and TeO5 Polyhedra in the same material

Two new tellurites, NH₄RbTe₄O₉·2H₂O and NH₄CsTe₄O₉·2H₂O have been synthesized and characterized. The compounds were synthesized hydrothermally, in near quantitative yields, using the alkali metal halide, TeO₂, and NH₄OH as reagents. The iso-structural materials exhibit layered, two-dimensional structural topologies consisting of TeO_x (x=3, 4, or 5) polyhedra separated by NH₄⁺, H₂O, Rb⁺ or Cs⁺ cations. Unique to these materials is the presence of TeO₃, TeO₄, and TeO₅ polyhedra. Thermogravimetric and infrared spectroscopic data are also presented. Crystal data: NH₄RbTe₄O₉·2H₂O: Monoclinic I2/a (no. 15), a=18.917(3) Å, b=6.7002(11) Å, c=21.106(5) Å, β=101.813(2)°, V=2618.5(9) Å³, Z=8; NH₄CsTe₄O₉·2H₂O: Monoclinic I2/a (no. 15), a=18.9880(12) Å, b=6.7633(4) Å, c=21.476(2) Å, β=102.3460(10)°, V=2694.2(3) Å³, Z=8.     

Transition-metal complexes of phenoxy-imine ligands modified with pendant imidazolium salts: Synthesis, characterisation and testing as ethylene polymerisation catalysts

Reaction between 3-((1R,2R)-2-{[1-(3,5-di-tert-butyl-2-hydroxy-phenyl)-meth-(E)-ylidene]-amino}-cyclohexyl)-1-isopropyl-4-phenyl-3H-imidazol-1-ium bromide (1a) or the derivative 3-((1R,2R)-2-{[1-(2-hydroxy-5-nitro-phenyl)-meth-(E)-ylidene]-amino}-cyclohexyl)-1-isopropyl-4-phenyl-3H-imidazol-1-ium bromide (1b) and metal halides MCl_x.yTHF (M = Zr, x = 4, y = 2; M = V, x = y = 3; M = Cr, x = y = 3), in THF, at −78 °C gives the metal complexes of general formula [MCl_x(κ²-N,O-OC₆H₂R¹R²C(H)N-C₆H₁₀-Im)₂][Br]₂ (where M = Zr, x = 2, R¹ = R² = ^tBu, 2; M = Zr, x = 2, R¹ = H, R² = NO₂, 3; M = V, x = 1, R¹ = R² = ^tBu, 4; M = Cr, x = 1, R¹ = R² = ^tBu, 5; M = Fe, x = 0, R¹ = R² = ^tBu, 6; Im = 1-isopropyl-4-phenyl-3H-imidazol-1-ium-3-yl). ¹H and ¹³C NMR spectroscopy of 2 and 3 indicate κ²-N,O-ligand coordination via the phenoxy-imine moiety with pendant imidazolium salt that is corroborated by a single crystal structure of 6. Compounds 2, 3, 4 and 5 were tested as precatalysts for ethylene polymerisation in the presence of methylaluminoxane (MAO) cocatalyst, showing low activity. Selected polymer samples were characterised by GPC showing multimodal molecular weight distributions.     

Segregated aromatic π-π stacking interactions involving fluorinated and non-fluorinated benzene rings: Cu(py)2(pfb)2 and Cu(py)2(pfb)2(H2O) (py = pyridine and pfb = pentafluorobenzoate)

The syntheses, physical characterization and crystal structures of two new molecular copper(II) complexes of composition [Cu(C₅H₅N)₂(C₇F₅O₂)₂] (1) and [Cu(C₅H₅N)₂(C₇F₅O₂)₂(H₂O)] (2) (C₅H₅N = py = pyridine and C₇F₅O₂⁻ = pfb = pentafluorobenzoate) are reported. Single-crystal X-ray structure determinations revealed that in 1, the Cu²⁺ ion, which lies on a crystallographic inversion centre, is coordinated to two py molecules and two oxygen atoms from two monodentate pfb anions, resulting in a trans-CuN₂O₂ square planar geometry. In 2, the Cu²⁺ ion is also coordinated to two py and two pfb species in addition to a water molecule in the apical site of a distorted CuN₂O₃ square pyramid. In the crystal packing, both 1 and 2 show segregated aromatic π-π stacking interactions in which (py + py) and (pfb + pfb) ring-pairings are seen, but no (py + pfb) pairings occur. Crystal data: 1: C₂₄H₁₀CuF₁₀N₂O₄, M_r = 643.88, space group , a = 8.0777 (3) Å, b = 8.0937 (3) Å, c = 10.5045 (5) Å, α = 90.916 (3)°, β = 93.189 (2)°, γ = 118.245 (3)°, V = 603.36 (4) Å³, Z = 1. 2: C₂₄H₁₂CuF₁₀N₂O₅, M_r = 661.90, space group , a = 7.5913 (5) Å, b = 15.6517 (6) Å, c = 21.1820 (14) Å, α = 95.697 (4)°, β = 94.506 (2)°, γ = 91.492 (4)°, V = 2495.2 (3) Å³, Z = 4.     

A variety of new tri- and tetranuclear Mn–Ln and Fe–Ln (Ln = lanthanide) complexes

The use of carboxylates in the synthesis of 3d/4f clusters, with or without a second organic ligand, has afforded a series of tetranuclear M₂Gd₂ complexes (M = Fe or Mn), and two new trinuclear M₂Gd (M = Fe or Mn) molecular compounds. Only one of these, [Mn₂Gd₂O₂(O₂CBu^t)₈(HO₂CBu^t)₄] (1), does not contain a multidentate chelate ligand. Two other similar tetranuclear clusters were synthesized from the use of triethanolamine (teaH₃) and 1,1,1-tris(hydroxymethyl)ethane (thmeH₃). [Mn₂Gd₂(OH)₂(O₂CPh)₄(NO₃)₂(teaH)₂] (2) has very similar structure with 1, bearing a defective incomplete double-cubane core bridged by μ₃-O atoms, whereas in the core of [NHEt₃]₂[Fe₂Gd₂(O₂CPh)₄(thme)₂(NO₃)₄] (3) the thme³⁻ ligand caps the two incomplete cubane units, providing the triply-bridging alkoxides needed for bridging. Two new oxide-centered triangular clusters were synthesized bearing the Schiff-based chelate 2-{[2-(dimethylamino)ethyl]methylamino}ethanol (dmemH), namely [Fe₂GdO(O₂CBu^t)₂(dmem)₂(NO₃)₃] (4), and [Mn₂GdO(O₂CBu^t)₂(dmem)₂(NO₃)₃] (5). Magnetic susceptibility measurements and/or reduced magnetization studies established that complexes 1 and 3 have an S = 5 ground state, complex 2 has S = 4, and complexes 4 and 5 are S = 7/2 in their ground states. These complexes portray the feasibility of obtaining products bearing metal cores commonly found in homometallic clusters, even when these include metals with completely different coordination chemistry and electronic structure, such as lanthanides.     

Asymmetric enamide hydrogenation in the synthesis of N-acetylcolchinol: a key intermediate for ZD6126

A synthesis of N-acetylcolchinol, a key intermediate in the synthesis of ZD6126, was developed. The enantiodifferentiating step required the catalytic asymmetric hydrogenation of an enamide. After screening a range of metal and ligand combinations it was found that (S,S)-ⁱPr-FerroTANE Ru(methallyl)₂ and [(S,S)-^tBuFerroTANE Rh(COD)]BF₄ gave both high enantioselectivity (>90% ee) and high catalyst utility (molar S/C = 1000).     

Preparation, crystal structure and photoluminescence of garnet-type calcium tin titanium aluminates

Colorless and transparent single crystals of Ca₃Sn_2.2Ti_0.8Al₂O₁₂, which emit blue-white light under ultraviolet light, were prepared by heating a mixture of oxides and calcium carbonate with a calcium and aluminum-rich composition at 1500 °C. Single crystal X-ray diffraction revealed that the crystal structure is the garnet-type with a cubic cell parameter (a=12.5309(3) Å) and the space group, Ia 3¯d (R1=0.0277, wR2=0.0663, and S=1.367 for all data). The structural formula is presented as Ca₃[Sn_0.96Ti_0.04]_octa[Al_0.67Ti_0.24Sn_0.09]_tetraO₁₂. Polycrystalline solid solutions of Ca₃Sn_3−xTi_xAl₂O₁₂ were prepared by solid state reaction in air at 1370 °C with nominal titanium contents from x=0.6 to 1.4. The refined unit cell parameter decreased with increasing x. A broad blue-white emission with a peak wavelength of 465 nm was observed for the solid solutions at room temperature.     

Structural characterization and catalytic properties of bis(1,1,3,3-tetramethylguanidinium) dichromate

The structure of bis(1,1,3,3-tetramethylguanidinium) dichromate was determined from powder X-ray diffraction data. The compound crystallizes in the monoclinic system (space group P2₁/n) with a = 10.79714 (15) Å, b = 11.75844 (16) Å, c = 8.15097 (11) Å, β = 109.5248 (6)°. The structure consists of dichromate anions (Cr₂O₇²⁻) stabilized by tetramethylguanidinium cations ([H₂NC(N(CH₃)₂)₂]⁺ or [TMGH]⁺). Phase transitions of [TMGH]₂Cr₂O₇ were determined by differential scanning calorimetry, thermal gravimetric analysis and in situ Raman spectroscopy, where the decomposition of the matrix into CrO_x was found at 171-172 °C. Further heat treatment to above 400 °C resulted in formation of the thermodynamically stable Cr₂O₃, most likely with the [TMGH]⁺ cation as reductant. The catalytic activity of [TMGH]₂Cr₂O₇ supported on TiO₂ anatase in the selective catalytic reduction (SCR) of nitrogen oxide was also investigated, however only moderate activity was observed in the temperature range 100-400 °C compared to the activity of e.g., vanadia supported on titania.     

Morphological and magnetic study of CaMnO3−x oxides obtained from different routes

The CaMnO_3−x (x=0 and 0.02) mixed oxide was synthesized from both thermal treatment of the [CaMn(C₃H₂O₄)₂(H₂O)₄] metallo-organic precursor and ceramic method. In the case of the latter method, temperatures of 1350 °C and 50 h were necessary; however, lower temperatures, 800 °C, and shorter reaction times, 15 h, were utilized in the attainment of the mixed oxide from the precursor. As a consequence, the morphology of the different products is clearly different. The samples exhibit three-dimensional antiferromagnetic ordering with T_N near 120 K, and a low-dimensional antiferromagnetic ordering at high temperatures. The presence of a ferromagnetic component above T_N was also observed in both compounds, it is slightly stronger in the phase prepared by the ceramic route.     

Structure and properties of the CaFe2O4-type cobalt oxide CaCo2O4

The calcium cobalt oxide CaCo₂O₄ was synthesized for the first time and characterized from a powder X-ray diffraction study, measuring magnetic susceptibility, specific heat, electrical resistivity, and thermoelectric power. CaCo₂O₄ crystallizes in the CaFe₂O₄ (calcium ferrite)-type structure, consisting of an edge- and corner-shared CoO₆ octahedral network. The structure of CaCo₂O₄ belongs to an orthorhombic system (space group: Pnma) with lattice parameters, a=8.789(2) Å, b=2.9006(7) Å and c=10.282(3) Å. Curie-Weiss-like behavior in magnetic susceptibility with the nearly trivalent cobalt low-spin state (Co³⁺, 3d, S=0), semiconductor-like temperature dependence of resistivity (ρ=3×10⁻¹ Ω cm at 380 K) with dominant hopping conduction at low temperature, metallic-temperature-dependent large thermoelectric power (Seebeck coefficient: S=+147 μV/K at 380 K), and Schottky-type specific heat with a small Sommerfeld constant (γ=4.48(7) mJ/Co mol K²), were observed. These results suggest that the compound possesses a metallic electronic state with a small density of states at the Fermi level. The doped holes are localized at low temperatures due to disorder in the crystal. The carriers probably originate from slight off-stoichiometry of the phase. It was also found that S tends to increase even more beyond 380 K. The large S is possibly attributed to residual spin entropy and orbital degeneracy coupled with charges by strong electron correlation in the cobalt oxides.