Chemiluminecsence in the oxidation of Na2C60 by the (NH4)2Ce(NO3)6 complex in THF

Chemiluminescence (_max = 790 nm) in the oxidation of fulleride Na₂C₆₀ by the (NH₄)₂Ce(NO₃)₆ complex in THF was found. The ³C₆₀* triplet of fullerene formed in the transfer of an electron from the intermediate C₆₀ ^– anion to Ce^IV was suggested to be the chemiluminescence emitter.     

Capillary zone electrophoresis of orotic acid in urine with on-line isotachophoresis sample pretreatment and diode array detection

Two hydroxide-selective microbore analytical columns (the Dionex AS11 and AS15) were tested and compared for the quantitation of anionic species in 30% hydrogen peroxide. The ions of interest were fluoride, acetate, formate, chloride, bromide, nitrate, sulfate, and phosphate. Statistically sound calibration and spiking studies were carried out, investigating the range of a blank to 60 ppb. Prior to injection onto the separators, peroxides were loaded without pretreatment onto a concentrator column, which was then washed with deionized water to remove the matrix. Although retention times gradually decreased during the spiking studies, reliable quantitation was still achievable on both columns at the target concentration of 30 ppb. However, various resolution problems meant that the AS11 should not be recommended for this application.     

New organic metals: Radical cation salts of bis(ethylenedioxo)tetrathiafulvalene with halide mercurate anions

Radical cation salts with halide mercurate anions were obtained by the electrochemical oxidation of bis(ethylenedioxo)tetrathiafulvalene (BEDO-TTF), and their conductivity was studied. The compounds (BEDO-TTF)₄Hg₃X₈ (X = Cl or Br), (BEDO-TTF)₄Hg_3.5I₉, and (BEDO-TTF)₂HgBr₃ possess the conductivity of the metallic type down to helium temperatures.Translated fromIzvestiya Akademii Nauk. Seriya Khimicheskaya, No. 5, pp. 1167–1170, May, 1996.     

Indyllithium and the Indyl Anion [InL]−: Heavy Analogues of N‐Heterocyclic Carbenes

Reduction of the indate complex In(NON^Ar)(μ‐Cl)₂Li(OEt₂)₂ (NON^Ar=[O(SiMe₂NAr)₂]^2?; Ar=2,6‐iPr₂C₆H₃) with sodium generates the In^II diindane species [In(NON^Ar)]₂. Further reduction with a mixture of potassium and [2.2.2]crypt affords the In^I N‐heterocyclic indyl anion [In(NON^Ar)]^?, which crystallizes with a non‐contacted [K([2.2.2]crypt)]⁺ cation. The indyl anion can also be isolated as the indyllithium compound In(NON^Ar)(Li{THF}₃), which contains an In?Li bond. Density functional theory calculations show that the HOMO of the indyl anion is a metal‐centred lone pair, and preliminary reactivity studies confirm its nucleophilic behaviour.     

Coordination Chemistry of Diiodine and Implications for the Oxidation Capacity of the Synergistic Ag+/X2 (X=Cl,Br, I) System

The synergistic Ag⁺/X₂ system (X=Cl, Br, I) is a very strong, but ill‐defined oxidant—more powerful than X₂ or Ag⁺ alone. Intermediates for its action may include [Ag_m(X₂)_n]^m+ complexes. Here, we report on an unexpectedly variable coordination chemistry of diiodine towards this direction: ( A )Ag‐I₂‐Ag( A ), [Ag₂(I₂)₄]²⁺( A ^?)₂ and [Ag₂(I₂)₆]²⁺( A ^?)₂?(I₂)_x≈0.65 form by reaction of Ag( A ) ( A =Al(OR^F)₄; R^F=C(CF₃)₃) with diiodine (single crystal/powder XRD, Raman spectra and quantum‐mechanical calculations). The molecular ( A )Ag‐I₂‐Ag( A ) is ideally set up to act as a 2 e^? oxidant with stoichiometric formation of 2 AgI and 2 A ^?. Preliminary reactivity tests proved this ( A )Ag‐I₂‐Ag( A ) starting material to oxidize n‐C₅H₁₂, C₃H₈, CH₂Cl₂, P₄ or S₈ at room temperature. A rough estimate of its electron affinity places it amongst very strong oxidizers like MF₆ (M=4d metals). This suggests that ( A )Ag‐I₂‐Ag( A ) will serve as an easily in bulk accessible, well‐defined, and very potent oxidant with multiple applications.     

烷基硫酸盐表面张力的量子化学研究

用AMl量子化学计算法优化了十三烷基硫酸根阴离子和——CH3在不同取代位的十二烷基硫酸根阴离子的几何构型，得到最优构型时最高占据分子轨道能级EHOMO、最低空轨道能级ELUMO、电子能量Eele和偶极矩μ等数据．将这些电子结构数据分别与表面张力相拟合，得到很好的相关性。文中讨论了——CH3在不同位置取代对表面张力的影响。     

Theoretical study on the structures and electronic spectra of TCNE2-.

Investigations into the charge-separated states and electron-transfer transitions in tetracyanoethylene (TCNE) complexes have recently generated much interest. In this work we present theoretical calculations showing that the most stable structure of the dianion TCNE2- has D2d symmetry in vacuum as well as in the solvents dichloromethane and acetonitrile. By means of the coupled cluster linear response, we compute the vertical electronic spectrum in both the gas phase and solution. The theoretical results are compared to the experimental data and good agreement is achieved.