Zur kenntnis von [O2]+[Mn2F9]−

[O₂]⁺[Mn₂F₉]^? has been prepared for the first time by reaction of MnO₂ or MnF_x (x = 2,3,4) with a mixture of fluorine and oxygen (P_F2/O₂ ≈ 300–3500 atm., t ≈ 350–550°C) either as a dark red powder or as ruby red needles or plates. From single crystal studies the space group is C2/c - C⁶_2h (No. 15) with a = 17.55₂, b = 8.37₃, c = 9.10₁ Å, β = 102.3°, Z = B (at ?150°C). The crystal structure has been refined to R = 0.053 (1619 unique reflections). From the structure determination [O₂]+[Mn₂F₉] has ‘mänder’ like bands of double chains of [MnF₆] octahedra, which are stacked up in layers parallel to (100) with O₂⁺-cations (d_0?0 = 1.10₀ Å) located between the layers. ν_O2 is at 1838 cm^?1 and the magnetic moment μ_eff = 5.63 B.M. is as expected for a ‘spin only’ case without spin-spin interaction.     

A low-energy passage for C+ + H2 → CH+(1Σ+) + H

Ab initio (SCF and CI) calculations have been performed for the linear approach (C_∝v) of C⁺ to H₂. For the ² Σ⁺ surface the saddle point and barrier height were determined. The interaction of the ²Σ⁺ and ²Π surfaces was investigated, leading to the conclusion that in near-C_∝v symmetry a low-energy path exists by which CH⁺¹ Σ⁺ can be formed, with negligible barrier in excess of endothermicity.     

新型微孔磷酸铝[C4N2H14]2+[H2Al3P3O14]2-的合成、结构及相转变

以3-甲氨基丙胺为结构导向剂,在水热条件下合成了1个具有三维开放骨架结构的微孔磷酸铝化合物[C4N2H14][H2Al3P3O14](1),并通过X射线单晶衍射确定了其结构,用粉末X射线衍射(PXRD)、热重(TG)、元素分析(ICP及CHN)和扫描电子显微镜(SEM)对其进行表征.结果表明,化合物1属正交晶系,Pbca空间群,晶胞参数a=1.59839(11)nm,b=0.99402(6)nm,c=1.82261(11)nm,V=2.8958(3)nm3.化合物1的无机骨架由铝氧多面体(AlO5/AlO6)和磷氧四面体(PO4)严格交替连接构筑而成,形成了在[010]方向上具有一维十元环孔道的三维阴离子开放骨架.每个P原子通过桥氧原子与相邻的4个Al原子相连,而Al原子除了通过桥氧原子与相邻的4个P原子相连之外,还通过羟基的桥氧原子与1个或2个Al原子相连,分别形成五配位和六配位的Al.化合物1在550℃空气或氧气气氛下灼烧5 h后转变为具有ATV分子筛结构的微孔磷酸铝分子筛AlPO4-25,且一直稳定到800℃.     

A model study of proton transfer in the H5O2 complex on a bidimensional potential energy surface

We have studied the hydrogen-bonded complex H₃O⁻-H₂O as a model for proton transfer in water. Quantum mechanical computations have been performed in two dimensions (the coordinates are the position of the hydrogen atom and the O-O distance, for a linear geometry), for investigating static and dynamical properties. The validity of the adiabatic separation of the O-O and O-H … O motions has been tested, showing that it holds only in a very restricted range of O-O distances. An initial wavepacket (created by an external perturbation), localized close to one of the two minima, is propagated in time. The proton flux is divided into two contributions, one along the reaction path and the other mainly due to tunnelling.     

Revised theoretical energy for the a 3Σg+ state of H2

The Born—Oppenheimer energy of H₂ in the a ³Σ_g⁺ state has been improved. The new result, with estimated values of the relativistic and nonadiabatic corrections, and with the previously computed adiabatic corrections yields T₀ = 95077.3 cm^?1 in a good agreement with the recent experimental value T₀ = 95076.4 ± 0.5 cm^?1 of Miller and Freund.     

Supramolecular Systems Based on Ca2+, [Mo3O2S2Cl6(H2O)3]2s-, [Mo3S4Cl6.75Br0.25(H2O)2]3s- and Cucurbit[6]uril

Adducts of cucurbit[6]uril with Ca²⁺ and trinuclear cluster chloroaquacomplexes (H₉O₄)₂(H₇O₃)₂[(Ca(H₂O)₅)2(C₃₆H₃₆N₂₄O₁₂)]Cl₈·0.67H₂O (1) and [(Ca(H₂O)₅)₂(C₃₆H₃₆N₂₄O₁₂)]× [Mo₃O₂S₂Cl₆(H₂O)₃]₂·13H₂O (2) are obtained and structurally characterized. The structures of both compounds contain polymeric [Ca(H₂O) _n ]₂² CB[6]∞ cations that form infinite columns; the space between them is filled with Cl^s- (1) and [Mo₃O₂S₂Cl₆(H₂O)₃]^2s- (2). A new (H₇O₃)₂(H₅O₂)× [Mo₃S₄Cl_6.25Br_0.25(H₂O)₂](C₃₆H₃₆N₂₄O₁₂)·CH₂Cl₂·6H₂O complex (3) is also obtained and structurally characterized.     

Zur kenntnis von [O2]22+[Ti7F30]2−

[O₂]²⁺₂[Ti₇F₃₀]^2? has been obtained by reaction of TiO₂ with a mixture of fluorine and oxygen (p_F2/O2 ≈ 300–3500 atm., t ≈ 300–450°C) either as colourless powder or in form of colourless, clear needles. From single crystal studies the spacegroup is P$\text{3}$ - C_3i¹ (No. 147) with a = 10.19₂, c = 6.50_o Å, Z = 1. The crystal structure has been refined to R = 0.086 [R_w = 0.058] (748 unique reflexions [F_o > 2σ(F_o)]). From the structure determination [O₂]²⁺₂[Ti₇F₃₀]^2? has isolated columns of partially distorted [TiF₆] octahedra (- column structure) which are connected only quite loosely by (disordered) O₂⁺ cations. ν_O2+ is at 1857 cm^?1, the magnetic moment μ_eff = 2.35 B.M. (295 K) is quite as expected for a ‘spin-only’ case.     

Potential energy surfaces for the photodissociation H2O→O(1Dg + H2(X1Σ+g)

The minimum energy pathways for symmetrical dissociation of water into O(¹D_g + H₂(X¹Σ⁺_g) are calculated by the MRD Cl technique for various excited states of H₂O and possible mechanism for the photodissociation are discussed.     

Stereoelectronic effects on cyclobutyl participation. The 10-tetracyclo[5.2.1.02,6.O3,9]decyl cation

While the solvolysis of tosylate 5c proceeds very rapidly to generate 4 or its rapidly equilibrating classical alternative, the epimeric compound 6c proved to be unreactive; bond orientation effects are implicated.     

Vibrational energy transfer in H2 + He

A semiclassical approach is developed to study vibrational energy transfer in H₂ + He by use of the a priori interaction potential including all nonzero impact parameter collisions. The calculated values of the rate coefficient are found to be in excellent agreement with experimental data which are available in the temperature ranges 60–450 K and 1350-3000 K. The temperature dependence is shown to seriously deviate from the Landau-Teller prediction below 1000 K. The calculation was carried out over the temperature range of 30 to 10000 K.     

Al(2Pu)+H2(X1Σ+g)的分子反应动力学

基于多体展式方法所导出的ＡｌＨ２（Ｘ＾２Ａ１）分析势能函数,用准经典的Ｍｏｎｔｅ－Ｃａｒｌｏ轨迹法对Ａｌ（＾２Ｐｕ）＋Ｈ２（Ｘ＾１∑＾＋ｇ,ｕ＝ｊ＝０）的分子反应动力学过程进行了计算。结果表明,此反应的主产物为交换反应Ａｌ（＾２Ｐｕ）＋Ｈ２（Ｘ＾１∑＾＋ｇ,ｖ＝ｊ＝０）→ＡｌＨ（Ｘ＾１∑＾＋,Ｖ’,ｊ’）＋Ｈ（＾２Ｓｇ）的ＡｌＨ（Ｘ＾１∑＾＋,ｖ’,ｊ’）没有发现ＡｌＨ２（Ｘ＾２Ａ１）的络合物。而     

The generation and identification of the transient vinylidene cation, [H2CC]+.

The vinylidene cation, [CH₂C]^+., was generated as a transient species by collisionally induced charge reversal of the corresponding anion. The collisionally induced mass spectrum of the transient [CH₂C]^+. is characteristically different from that of ionised acetylene.     

Aggregates of complexes [Sc(H2O)4(NCS)2]+ and [Sc(H2O)2(NCS)4]? with 18-crown-6

The compounds [Sc(H₂O)₄(NCS)₂][Sc(H₂O)₂(NCS)₄] ·2(18C6) (I) and [Sc(H₂O)₄(NCS)₂][Sc(H₂O)₂(NCS)₄] · 3(18C6) · H₂O (II) were synthesized and studied by X-ray diffraction analysis. It was found that the cations in the structures of compounds I and II form sandwiches [Sc(H₂O)₄(NCS)₂] · 2(18C6). In the case of I, the sandwiches are united by the [Sc(H₂O)₂(NCS)₄]⁻ anions into chains, while in compound II, the sandwiches and infinite chains of [Sc(H₂O)₂(NCS)₄] · 18C6 · H₂O are bonded by van der Waals contacts only. Original Russian Text ? A.B. Ilyukhin, S.P. Petrosyants, 2007, published in Koordinatsionnaya Khimiya, 2007, Vol. 33, No. 4, pp. 275–281.     

A State-selected study of the symmetric charge transfer reaction H2+ + H2

We have measured the relative total charge transfer cross sections of H₂⁺ + H₂ as a function of the vibrational state of H₂⁺, υ′_o = 0–4. using the crossed ion-neutral beam and high-resolution photoionization methods. The experimental results obtained at a center-of-mass collisional energy of 22.5 eV are found to be in excellent agreement with a recent theoretical study.     

CAS SCF Cl calculations for the 3Σ−g, 1Σ+g, 3Σ+u, and 5Δu states of Sc2

CAS SCF CI (SD) calculations have been carried out for the ³Σ^?_g, ¹Σ⁺_g, ³Σ⁺_u, and ⁵Δ_u states of Sc₂ using large gaussian basis sets. The ³Σ^?_g, ¹Σ⁺_g, and ³Σ⁺_u states arise from the ²D(4s² 3d¹) + ²D(4s² 3d¹) limit of Sc₂ and are found to be only weakly bound (D_c ≈ 0.06 eV and R_c ≈ 8.0a₀). The ⁵Δ_u state arises from the ²D(4s² 3d¹) + ⁴F(4s¹ 3d¹ 4p¹) atomic limit. This state is found to be strongly bound relative to its limits (D_c ≈ 0.8 eV and R_c ≈ 7.0a₀).     

Collision rotational transfers in NaH A1Σ+ by He,Ar or H2 (and in KH A1Σ+ by H2)

The total and relative rotational transfer cross sections σ_total and σ_Ji-Jf, by collisions of NaH A¹Σ with He, Ar or H₂, are measured from υ′ = 4 and υ′ = 11, J₁′ = 6. The σ_total increase as υ′ increases. They are similar for He and H₂ but much greater for Ar especially at large υ′. In NaH A¹Σ⁺ the bond goes from covalent to ionic as υ′ increases: σ_total is very sensitive to an attractive potential due to the interaction of the permanent electric dipole moment of the molecule with the polarizability of the atom (α_Ar = 11 au, α_He = 1.37 au). The σ_Ji-Jf decrease monotonously as |J_f-J_i| increases and may be fitted by a scaling law. The variation with ΔJ depends on the colliding gas but does not change appreciably with υ′: most of the transfers could take place on the repulsive part of the interaction potential, the shape of which would not depend on υ′.     

微量热法研究 [Cu(phen)2]2+、[Cu(bpy)2]2+与DNA的作用

用微量热法对菲咯啉合铜([Cu(phen)     

具有[344484]笼状结构单元的微孔磷酸镓Ga3P2O8(OH)3(H2O)的合成、晶体结构及表征

Open-framework metal phosphates have been the subject of intense research owing to their interesting structural chemistry and potential applications in catalysis and ion exchange. The gallium phosphate family has exhibits rich structural chemistry. A novel gallium phosphate Ga₃P₂O₈(OH)₃(H₂O)(GaPO-CJ36) has been prepared in a hydrothermal reaction system of GaO(OH)-H₃PO₄-Co(chxn)₃Cl₃-H₂O at 180 ℃ for 7 days. Single-crystal X-ray analysis shows that GaPO-CJ36 crystallizes in the P2₁/c space group with a=1.833 35(12) nm, b=0.503 94(3) nm, c=1.062 90(9) nm, V=0.982 01(12) nm³, and Z=4. The connection of GaO₂(OH)₃(H₂O) octahedra, PO₄ and GaO₄ tetrahedra through vertex oxygen atoms forms a three-dimensional open framework, which contains 8-ring channels along the [010] direction. Its structure is composed of interesting [3⁴4⁴8⁴] cages, which have not been found in known gallium phosphates. CSD: 416779.     

A non-empirical LCAO-SCF-MO investigation of cross sections through the potential energy surface for the [C2H2Cl]+ systems; comparison with the [C2H5+] and [C2H4F]+ systems

Non-empirical LCAO MO SCF calculations are reported on cross sections through the C₂H₄Cl⁺ system and comparisons are drawn with the C₂H₅⁺ and C₂H₄F⁺ systems. Barriers to rotation in the classical 1- and 2-substituted ethyl cations have been computed and an investigation made of the bridged chloronium and fluoronium ions. The results suggest that the relative stabilities of bridged ions with respect to the corresponding classical 2-substituted ethyl cations increase in the order H < F < Cl. The results are discussed in terms of available experimental data and consideration given to correlation and solvation energy effects.     

[SiCu(H2O)W11O39]6-在玻碳电极上的多层组装及电催化性能

The electrochemical behavior of SiCu W11 heteropolyacide in acidic aqueous solution was studied. The effect of solution pH on the electrochemical behavior of SiCu W11 was discussed and the mechanism was suggested. New electrode was modified by muhilayer films composed of heteropolyanion (SiCu W11 and cationic polymer poly (diallyldimethylammonium chloride). Cyclic vohammetry showed the uniform growth of the film. The modified electrodes exhibited some special electrochemical properties in the films, different from those in homogeneous aqueous solutions. The effect of pH on the redox behavior of SiCu W11 in the films was discussed in details. The muhilayer film electrodes have an excellent electrocatalytic response to the reduction of BrO3^- and NO2^-.