焦磷酸盐水溶液中稳定Pr(IV)和Tb(IV)的研究

本文报道了在焦磷酸盐的碱性水溶液中用O~3氧化Pr(III)和Tb(III),从而得到Pr(IV)-P~2O~7^4^-和Tb(IV)-P~2O~7^4^-的配合物溶液,通过对溶液进行化学分析及吸收光谱的研究,证明了溶液中有Pr(IV)和Tb(IV)的存在,其持征吸收分别为λmax=365nm,摩尔消光系数ε=1205L/mol.cm;/.pr(iv)=257nm,ε=929L/mol.cm.在碱性条件下,Pr(IV)和Tb(IV)的还原反应均为拟一级反应.用动力学方法测定了不同条件下Pr(IV)和Tb(IV)的还原速率常数和半衰期,从而探讨了稳定Pr(IV)和Tb(IV)的条件.同时还测定了在反应条件下Pr(IV)/Pr(III)和Tb(IV)/Tb(III)电对的克式电位。     

Crystal structures of hafnium(IV) and zirconium(IV) complexes with β-diketones

Preparation methods are developed for a number of 7- and 8-coordinated derivatives of Hf(IV) and Zr(IV) with β-diketonate ligands (R¹-CO-CH-CO-R²). The complexes obtained are examined by IR spectroscopy, mass spectrometry, and X-ray crystallography. All structures are molecular. The M-O distances fall within 2.09–2.28 Å. In the crystals, the molecules are joined only by van der Waals interactions. It is demonstrated that the series of hafnium(IV) and zirconium(IV) chelates with identical ligands are isostructural, and the introduction of CF₃- or tert-butyl groups in the terminal positions of the ligand as well as chlorine substitution for one of the ligands do not essentially affect the basic geometric characteristics of the ligand in the complexes.     

Electrochemical Behavior of Novel Bis(β-diketonate)phthalocyanine Complexes of Zr(IV) and Hf(IV)

We have used cyclic voltammetry to study the electrochemical properties of novel bis(-diketonate)phthalocyanine complexes of Zr(IV) and Hf(IV) in dichloromethane. We found three waves for the studied complexes that can be attributed to one-electron processes MPc(L)^0/1– ₂, MPc(L)^1+/0 ₂ and MPc(L)^2+/1+ ₂. We have shown that the electrochemical behavior of the complexes depends on the nature of the substituents in axial ligands and does not depend on the nature of the metals. We have analyzed the stability of the one-electron oxidation products of the complexes relative to disproportionation.     

Über das Hydroxylammonium-Fluorotitanat(IV)

Summary The microcristalline phase (NH₃OH)₂TiF₆ has been isolated from aqueous solution. It crystallizes in the tetragonal system with cell parameters:a=9.654±0.005 Å,c=11.546±0.010 Å. The hydroxylammonium fluorotitanate was characterized by vibrational spectroscopy and its thermal decomposition studied by DSC and TG analysis.

     

Titanium(IV)–EDTA complex

This work aims the evaluation of the kinetic triplets corresponding to the two successive steps of thermal decomposition of Ti(IV)–ethylenediaminetetraacetate complex. Applying the isoconversional Wall–Flynn–Ozawa method on the DSC curves, average activation energy: E=172.4±9.7 and 205.3±12.8 kJ mol^–1, and pre-exponential factor: logA=16.38±0.84 and 18.96±1.21 min^–1 at 95% confidence interval could be obtained, regarding the partial formation of anhydride and subsequent thermal decomposition of uncoordinated carboxylate groups, respectively. From E and logA values, Dollimore and Málek methods could be applied suggesting PT (Prout–Tompkins) and R3 (contracting volume) as the kinetic model to the partial formation of anhydride and thermal decomposition of the carboxylate groups, respectively.     

Bis(2,4–pentanedionato)vanadium(IV) aryloxides

Complexes of composition [VCl(acac)2(OAr1–4)] and [V(acac)2(OAr1–4)2] (HOAr1=HOC6H4NO2–4, HOAr2= HOC6H4OMe-4, HOAr3=HOC6H4But-4 and HOAr4= HOC6H2But-2,6–Me-4; acac=2,4–pentanedionato ion) have been synthesized by the reaction of [VCl2(acac)2] with the respective phenols or their trimethylsilyl derivatives. The complexes have been characterized by physicochemical and spectroscopic techniques. They are non-electrolytes in nitrobenzene. Room temperature magnetic moments in the 1.71–1.82B range are consistent with the VIV system. The reactions of [VCl(acac)2(OAr2)] and [VCl(acac)2(OAr3)] with chloride acceptors have been studied by conductance techniques and the formation of ionic complexes of the types [V(acac)2(OAr2,3)][MCl4] (M=Fe, Al or Sb) and [V(acac)2(OAr2,3)][MCl6] (M=P or Sb) is indicated by the conductance composition curves. Several of these complexes have been isolated and characterized.     

二丁基锡(IV)磺酸酯催化合成缩醛(酮)

用二丁基氧化锡与苯磺酸、甲磺酸反应制备了两种新的有机锡化合物——二丁基锡(IV)磺酸酯. 以二丁基锡(IV)磺酸酯作催化剂, 合成了一系列缩醛(酮), 并通过正交实验, 优化了有机锡催化缩醛(酮)合成反应的反应条件. 实验表明该催化反应产率高, 反应时间短, 催化剂用量少且能回收再利用.     

Polyfluorophenylaminosilane–Titanium (IV) Chloride Adducts

Si(NHC₆H_5-nF_n)₄.xTiCl₄ [n = 2–5; x = 3,4] are obtained from the disproportionation reactions between (CF₃CH₂O)₃SiNHC₆H_5-nF_n (n = 2–5) and TiCl₄ in petroleum ether (40–60°C) at 0°–10°C. These complexes are characterized by elemental analyses and IR, ¹H, and ¹⁹F NMR spectroscopy. Unlike the reported⁵ complex Si(NHC₆H₄F-o)₄.3TiCl₄, these are non-ionic in nature. All complexes give double adducts with CH₃NO₂ and CH₃CN within 24 h.     

Photochemistry of tetramethyl(2,2′-bipyridine)platinum(IV)

It is shown that photolysis of [PtMe₄(bipy)] using incident radiation with λ 436 or 473 nm occurs with high quantum efficiency of 0.8–1.0 to give homolysis of a methylplatinum bond; this has allowed a study of the chemical reactions of the [PtMe₃(bipy)] radical.     

Copper(II) and oxovanadium(IV) complexes of α-hydroxymethylserine

Summary Potentiometric and spectroscopic measurements were used to characterize the binding ability of -hydroxy-methylserine (Hms) with copper(II) and oxovanadium(IV) ions. The ligand was found to be generally a more efficient chelating agent than serine. Both of the deprotonated hydroxyl groups of Hms can be involved in coordination to vanadyl ions, whereas copper(II) binds in the same way as with serine.     

Facile and Reversible Formation of Iron(III)–Oxo–Cerium(IV) Adducts from Nonheme Oxoiron(IV) Complexes and Cerium(III)

Ceric ammonium nitrate (CAN) or Ce^IV(NH₄)₂(NO₃)₆ is often used in artificial water oxidation and generally considered to be an outer-sphere oxidant. Herein we report the spectroscopic and crystallographic characterization of [(N4Py)Fe^III-O-Ce^IV(OH₂)(NO₃)₄]⁺ ( 3 ), a complex obtained from the reaction of [(N4Py)Fe^II(NCMe)]²⁺ with 2 equiv CAN or [(N4Py)Fe^IV=O]²⁺ ( 2 ) with Ce^III(NO₃)₃ in MeCN. Surprisingly, the formation of 3 is reversible, the position of the equilibrium being dependent on the MeCN/water ratio of the solvent. These results suggest that the Fe^IV and Ce^IV centers have comparable reduction potentials. Moreover, the equilibrium entails a change in iron spin state, from S=1 Fe^IV in 2 to S=5/2 in 3 , which is found to be facile despite the formal spin-forbidden nature of this process. This observation suggests that Fe^IV=O complexes may avail of reaction pathways involving multiple spin states having little or no barrier.     

Synthesis and Characterization of Chlorobis(cyclopentadienyl) Titanium(IV) and Zirconium(IV) O,O’-Dialkyl and Alkylene Dithiophosphates

Abstract

Reactions of O,O′-dialkyl and alkylene dithiophosphoric acids with bis (cyclopentadienyl) titanium(IV) and zirconium (IV) dichloride in a 1:1 molar ratio in refluxing benzene proceeds with elimination of HCl and formation of the substituted derivatives, Cp₂MCl[S₂P(OR)₂] (where R = Et, Pr-n, Pr-i, Bu-i and Ph), Cp₂MCl[S₂POGO] (where G = ?CH₂CMe₂CH₂?, ?CH₂CEt₂CH₂? and ?CMe₂CMe₂?), (M = Ti and Zr). The complexes are dark red and yellow solids, soluble in common organic solvents and monomeric in nature. These have been characterized on the basis of elemental analyses, molecular weight determinations, IR, and NMR (¹H, ¹³C, and ³¹P).

GRAPHICAL ABSTRACT      

Die Bestimmung von Uran(VI) neben Uran(IV), Eisen(II, III), Vanadium (III, IV, V), Molybd?n (IV, VI) und Kupfer (II)

Ohne Zusammenfassung     

Titrationen mit Blei(IV)-acetatl?sungen

Ohne Zusammenfassung     

Spectroscopic,electrocatalytic, and photoelectrochemical characteristics of mixed-ligand bis(β-dicarbonylato) phthalocyanine complexes of zirconium(IV) and hafnium(IV)

The electronic absorption (EAS) and fluorescence spectra and electrocatalytic and photoelectrochemical characteristics of mixed-ligand complexes of zirconium(IV) and hafnium(IV) based on phthalocyanines in solutions and in thin films were investigated. It was established that a significant bathochromic shift of the Q band and redistribution of the intensities in the absorption bands are observed in the electronic absorption spectra. It was shown that films of the synthesized compounds are promising for use as photosensitizers and electrochemical sensors for oxygen in solution. __________ Translated from Teoreticheskaya i éksperimental’naya Khimiya, Vol. 44, No. 3, pp. 133–137, May–June, 2008.     

Structural study of bis(η-cyclopentadienyl)dicarbonyliron (p-tolyl)tin(IV) bromide

The compound, [η-C₅H₅Fe(CO)₂]₂(p-CH₃C₆H₄)SnBr, crystallizes in the monoclinic space group P2₁/c with a 9.643, b 12.016, c 19.205 Å, β 98.68°, V 2225.9 ų, and Z = 4. The crystal and molecular structures have been solved by use of the Patterson method. A full-matrix least-squares refinement led to a final R value of 0.036 for 3260 independent observed reflections. The electronic structure was calculated by use of the EHMO quantum chemical method. The molecular features and the influence on the coordinate geometry, and the nature of the bonding of the central tin atom are discussed.     

Reactions of bis(cyclopentadienyl)titanium(IV) and zirconium(IV) chlorides with 1,1′-diacetylferrocenyl bis(hydrazones). Formation of trimetallic derivatives

Bis(cyclopentadienyl)titanium(IV) and zirconium(IV) chlorides react with bis(hydrazones) derived from 1,1-diacetylferrocene in anhydrous THF in the presence of base to give complexes of the type [(Cp₂MCl)₂L] [M = Ti or Zr; LH₂ = ferrocenyl bis(hydrazones)]. Tentative structures are proposed for these complexes based upon elemental analyses, electrical conductance, magnetic moment and spectroscopic data.     

可溶性锰(IV)化学发光反应的研究

发现了在甲醛存在的条件下, 可溶性锰(IV)与30余种有机物和无机物的化学发光反应. 以头孢菌素类药物(头孢曲松钠、头孢唑啉钠、头孢拉定和头孢哌酮钠)为分析对象优化了可溶性锰(IV)-甲醛-头孢菌素类药物化学发光反应的条件, 建立了测定四种头孢菌素类药物的流动注射化学发光新方法, 并将建立的方法用于药物制剂中头孢菌素类药物的含量测定．同时, 对化学发光反应的机理进行了初步探讨.     

THE CRYSTAL STRUCTURE OF DI-μ-CHLORO-HEXACHLORO-BIS (ETHYL-CYANOFORMATE-N) DITITANIUM (IV)

Abstract

Crystals of the adduct titanium tetrachloride-ethylcyanoformate (1–1) are monoclinic a =9.06 Å, b =18.36 Å, c =13.83 Å, β =113°.2, space group C2/c, Z =8. The structure was solved by application of X-Ray diffraction techniques at room temperature. Atomic positions were refined by a full-matrix least-squares method to a final R of 0.049 using 829 non-zero independent reflections. This compound is dimeric with a double chlorine bridge between titanium atoms. Titanium is octahedrally coordinated to five chlorine atoms and to the nitrogen atom of the nitrile group and not to the oxygen atom of the carbonyl group. Thus in this complex the nitrogen atom is a better donor than the carbonyl oxygen.     

Mössbauer study of sodium ferrates(IV) and (VI)

Sodium ferrates(IV) and (VI) were synthesized by the reaction between Fe₂O₃ and Na₂O₂ in a dry oxygen stream. The Mössbauer data for the obtained samples are presented (for Na₂FeO₃–=0.18(2) mm/s; for Na₄FeO₅–=–0.54(2) mm/s). It was shown that pure K₂FeO₄ and Cs₂FeO₄ can be obtained by heating Fe₂O₃ with apropriate alkali metal peroxides.