Rapid and Sensitive Spectrophotometric Determination of Hafuium(IV) With 2-(5-Bromo-2-Pyridylazo)-5-Diethylaminophenol

Abstract

Hafnium(IV) reacts with 2-(5-bromo-2-pyridylazo)-5-diethylaminophenol in the pH range 3.3–11.0 to yield a sparingly soluble red-coloured chelate that can be dissolved with Triton X-100. Effect of initial pH of metal ion and order of addition of reagents was studied in detail. The 1:3 complex adheres to Beer's law over the concentration range 0.02–1.12 μg/ml of Hf(IV), has a molar absorptivity 1.33x10⁵ 1 mol^?1cm^?1, Sandell sensitivity 1.3 ng cm^?2, formation constant (log K) 11.94 and the method had a relative standard deviation of ± 1.5%. Effect of 60 diverse ions on the determination of hafnium(IV) was studied. This fairly selective method is the most sensitive so far reported for the spectrophotometric determination of hafnium(IV).     

Bismuth‐ and Hafnium‐Catalyzed Hydroamination of Vinyl Arenes with Sulfonamides,Carbamates, and Carboxamides

Catalytic intermolecular hydroamination of vinyl arenes is described. Our initial investigation revealed that a Bi(OTf)₃/[Cu(CH₃CN)₄]PF₆ system previously developed for catalytic intermolecular hydroamination of 1,3‐dienes was suitable for hydroamination of a styrene with sulfonamides, but the substrate generality of this system was unsatisfactory. Several metals were screened to expand the substrate scope, and a new Hf(OTf)₄/[Cu(CH₃CN)₄]PF₆ system was determined to be highly suitable. The combination of Hf(OTf)₄ and [Cu(CH₃CN)₄]PF₆ efficiently promoted the hydroamination of various vinyl arenes, including less‐reactive vinyl arenes with electron‐withdrawing groups. This strategy was applied to sulfonamides, carbamates, and carboxamides, and products were obtained in up to 99 % yield with 0.3–10 mol % catalyst loading.     

Synthesis and structural investigation of hafnium(IV) complexes with acetylacetone and trifluoroacetylacetone

Two volatile hafnium(IV) complexes with acetylacetone and trifluoroacetylacetone (HL) have been prepared and their structures have been studied at ?30°C. Crystal data for C₂₀H₂₈HfO₈: a = 21.5493(4) Å, b = 8.36720(10) Å, c = 13.9905(3) Å; β = 116.5550(10)°, space group C2/c, Z = 4, d _calc = 1.692 g/cm³, R = 0.015. Crystal data for C₂₀H₁₆F₁₂HfO₈: a = 8.1039(12) Å, b = 11.4499(14) Å, c = 15.790(2) Å; α = 99.341(4)°, β = 103.175(4)°, γ = 108.185(4)°, space group P?1, Z = 2, d _calc = 2.003 g/cm³, R = 0.074. Both structures are molecular and comprise isolated complex molecules HfL₄. The hafnium atom is coordinated with eight oxygen atoms of four β-diketonate ligands, Hf-O distances varying from 2.153 Å to 2.191 Å. The molecules make van der Waals contacts in the structures.     

Phase formation in the Dy2O3-HfO2-MoO3 system. Crystal structure of the new binary molybdate Dy2Hf2(MoO4)7

Phase relations have been studied for the subsolidus region of the Dy₂O₃-HfO₂-MoO₃ system; binary molybdates, Dy₂Hf(MoO₄)₅ and Dy₂Hf₂(MoO₄)₇, were found to form. The crystal structure of the latter has been solved (a = 20.661(3) , b = 9.816(1) , c = 13.796(3) , = 113.47(1)°, Z = 4, space group C2/c, R = 0.023) and found to be a new type of structure. In the structure, MoO₄ tetrahedra are linked by their vertices with HfO₆ octahedra and DyO₈ tetragonal antiprisms to form a 3D open-work, in which one can isolate double-row tetrahedral and octahedral chains extended down the c axis.Original Russian Text Copyright © 2004 by S. F. Solodovnikov, B. G. Bazarov, E. Yu. Badmaeva, Yu. L. Tushinova, E. S. Zolotova, and Zh. G. BazarovaTranslated from Zhurnal Strukturnoi Khimii, Vol. 45, No. 4, pp. 692–697, July–August, 2004.This revised version was published online in April 2005 with a corrected cover date.     

Diantipyrilmethane as complex-forming reagents in the thin-layer chromatographic determination of metals

Summary The efficiency of diantipyrilmethane used as a reagent for the chromatographic separation of metals, including titanium, zirconium and hafnium, rare earth elements, transition and platinum metals is shown. The peculiarities of the chromatographic behaviour of metal diantipyrilmethanates and the mechanism of their retention in TLC are discussed. Methods were developed for the determination of metals based on complex formation directly in the sorbent layer or by liquid extraction. The chromatographic separation takes place in silica gel thin layers with elution by organic solvent-mineral acid mixtures. The metals are determined by densitometric or spectrophotometric methods. After the complexes are isolated from the layer. The procedures are characterized by simplicity, efficiency, and a rather high selectivity. They were used to analyze steels, alloys, industrial solutions and other samples.     

Die Kristallstruktur von KPdMIVF7 (MIV = Zr,Hf)

The Crystal Structure of KPdM^IVF₇ (M^IV = Zr, Hf) Blue single crystals of KPdZrF₇ are obtained by heating the binary fluorides in sealed Pt-tubes under dry argon (solid state reaction, T ≈? 720°C, t ≈? 14 d). The compound crystallizes orthorhombically in the space group Pnna-D (Nr. 52); lattice parameters are a = 1 132.3(5) pm, b = 797.5(2) pm, c = 639.8(1) pm; Z = 4 (Four cycle diffractometer data, AED2). According to [F₄PdF_2/1ZrF₅] distortet [PdF₆]-octaedra are connected with pentagonal-bipyramidal [ZrF₇]-polyhedra via two bridging F^?, resulting in [PdZrF₁₁]-groups. These [PdZrF₁₁]-groups built up a threedimensional-network with K⁺ in its spacings. KPdHfF₇ crystallizes isotypically (a = 1 136.1(3) pm, b = 796.4(2) pm und c = 638.8(1) pm; four cycle diffractometer data, AED2).     

Zum chemischen Transport von ZrO2 und HfO2 mit den Transportmitteln Cl2 und TeCl4

On the Chemical Transport of ZrO₂ and HfO₂ with the Transport Agents Cl₂ and TeCl₄ ZrO₂ und HfO₂ migrate in a temperature gradient (1100 → 1000°C) with the transport agent either Cl₂ or TeCl₄ by endothermic transport reaction. At experiments in silica glass tubes with TeCl₄ well developed crystals of ZrO₂ could be obtained. From HfO₂, as from both oxides using Cl₂, only powdery products are formed. The transport rates with TeCl₄ were higher than with Cl₂. The influence of different pressures was examined for the transport of ZrO₂ with TeCl₂ with thermochemical model calculations the expected transport rates could be investigated. The large correspondence between calculated and experimental received values speaks for a true interpretation of the transport observations.     

The Separation of Zirconium and Hafnium by Liquid-Liquid Partition of their Thiocyanates

The partition equilibria of zirconium and hafnium thiocyanates between water and methyl isobutyl ketone have been studied under various conditions. Since the system shows extremely marked deviations from Nernst's distribution law, the two elements cannot be prepared in a very pure state by a simple multi-stage partition. By the use of suitable additives and a new scheme of material flow, however, a continuous process using 23 mixer settlers has been developed, by means of which ZrO₂ containing less than 10 p.p.m. of HfO₂ and HfO₂ containing only 0.3% of ZrO₂ can be obtained from a zirconium-hafnium mixture (hafnium content: 1 to 2%).     

Synthesis,crystal structure,and electrical properties of the new ternary molybdate Rb<Subscript>5</Subscript>NdHf(MoO<Subscript>4</Subscript>)<Subscript>6</Subscript>

The subsolidus phase relations in the ternary salt system Rb₂MoO₄-Nd₂(MoO₄)₃-Hf(MoO₄)₂ were studied by X-ray powder diffraction. The ternary molybdates Rb₅NdHf(MoO₄)₆ (1) and Rb₂NdHf₂(MoO₄)_6.5 are formed in this system. Compound 1 without impurities was synthesized by the solid-phase method by varying the temperature in the range of 400–600 °C and the annealing time from 70 to 110 h. Single crystals of compound 1 were grown by the flux method. The structure of compound 1 was established and the electrical properties of ceramic samples of this compound were investigated. This ternary molybdate has mixed electronic-ionic conductivity with the ionic component predominating at 200–500 °C. Published in Russian in Izvestiya Akademii Nauk. Seriya Khimicheskaya, No. 11, pp. 2063–2066, November, 2007.     

Insertion reactions of phenyl isocyanate into hafnium nitrogen bonds: synthesis and reactivity of hafnium complexes bearing substituted pyrrolyl ligands

A bis(diethylamido)hafnium compound [C₄H₃N(CH₂NMe₂)-2]₂Hf(NEt₂)₂ (1) has been prepared in 79% yield by reacting Hf(NEt₂)₄ with 2 equiv. of [C₄H₃NH(CH₂NMe₂)-2] in heptane via deamination. Reacting compound 1 with 2 equiv. of phenyl isocyanate at room temperature in diethyl ether results in the PhNCO being inserted seletively into hafnium-NEt₂ bonds to generate [C₄H₃N(CH₂NMe₂)-2]₂Hf[PhNC(NEt₂)O]₂ (2) in 56% yield. Similarly, while reacting 1 with 2 equiv. of phenyl isocyanate for a week in toluene produces a mixture of 2 and [C₄H₃N(CH₂NMe₂)-2]Hf[PhNC(NEt₂)O]₃ (3). For comparison, reacting Hf(NEt₂)₄ with 4 equiv. of PhNCO in a toluene solution at room temperature results in the PhNCO inserted into Hf-N bonds, and forms a tetrakis-ureato hafnium compound Hf[PhNC(NEt₂)O]₄ (4) in 88% yield. A theoretical calculation found that the unpaired electrons of the ureato fragments of 2 are resonance delocalized between the C-O, C-NPh, and C-NEt₂ bonds, which are all partially doubly bonded.