Reactivity of C10H7+ and C10D7+ with H2 AND D2

We have investigated, both theoretically and experimentally, the reactions of naphthylium C10H7+ and d-naphthylium C10D7+ ions with H2 and D2. Cross sections as functions of the collision energy have been measured for a variety of reaction channels. Theoretical calculations have been carried out at the density functional theory level which utilizes the hybrid functional B3LYP and the split-valence 6-31G* basis set. The key features of the potential energy surfaces and the relevant thermochemical parameters have been calculated and they provide insights on the reaction mechanisms. The bimolecular reactivity of C10H7+ with H2 is dominated by the production of naphthalene cation C10H8+. The reaction is not a direct atom-abstraction process, but instead it proceeds via the formation of a stable intermediate complex C10H9+ of sigma type geometry, with a significant mobility of hydrogen along the ring. This mobility allows the scrambling of the hydrogen atoms and causes the successive statistical fragmentation of the complex into a variety of product channels. Elimination of one H(D) atom appears to be favored over elimination of one H2 or HD molecule. Alternatively, the intermediate complex can be stabilized either by collision with a third body or by emission of a photon.     

DODMAC/n-C10H21OH/10%n-C10H22/H2O体系溶致液晶的2HNMR和SAXS研究

50℃下, 测定了双十八烷基二甲基氯化铵DODMAC/n-C10H21OH/10%n-C10H22/H2O四元体系相图, 确定了液晶区域范围, 用2H NMR方法, 并辅以偏光显微镜照片, 确定了液晶为反相六角状, 用SAXS求出了液晶晶面间距, 确定了晶面间距d1与含水量fw/(1-fw)之间的线性关系, 并求得圆柱形聚集体的直径ds=4.035nm.     

Unexpectedly facile isomerisation of [7,10-Ph2-7,10-nido-C2B10H10]2- to [7,9-Ph2-7,9-nido-C2B10H10]2-

The 2e-reduction of 1,12-Ph2-1,12-closo-C(2)B(10)H(10) followed by oxidation or metallation gives products that arise from [7,9-Ph2-7,9-nido-C(2)B(10)H(10)](2-), formed by unexpectedly facile isomerisation of the kinetic 7,10-isomer: the 4,1,6-MC(2)B(10) compounds which result are progressively isomerised to 4,1,8- and 4,1,12-isomers for M = {CpCo} but to an equilibrium mixture of 4,1,8- and 4,1,12-isomers for M = {(arene)Ru}.     

Synthesis of 2-I-closo-B10H92- by Iodination of closo-B10H120-

A pure salt 2-I-B₁₀H₉ ^{2 -}[N⁺(C₄H₉)4]₂ was obtained by treatment of ethanolic Na2⁺B10H₁ ² ₀ ^- with ethanolic iodine at -75°C, followed by addition of tetrabutylammonium bromide.     

Thermal transformations of B10H12(NH3)2, B10H12(C5H5N)2, and B10H12(C9H7N)2

Conclusions For B₁₀H₁₂L₂, where L=NH₃, C₅H₅N, or C₉H₇N, features of thermal transformations in the range 25–850°C and the composition of the pyrolysis products are determined. The latter are x-ray amorphous phases, containing nitride, carbide, boron carbide, boron, and carbon.Translated from Izvestiya Akademii Nauk SSSR, Seriya Khimicheskaya, No. 11, pp. 2481–2484, November, 1988.     

The structures of MeP(C2B10H10)2CH2 and MeAs(C2B10H10)2, compounds containing o-carborane ring carbon atoms in the heterocycle

Conclusions Crystal and molecular structures have been determined for 1-methylphospha-2,3,5,6-bis-o-carboranocyclohexane and 1-methylarsa-2,3,4,5-bis-o-carboranocyclopentane.Translated from Izvestiya Akademii Nauk SSSR, Seriya Khimicheskaya, No. 7, pp. 1523–1528, July, 1979.     

(C_2H_(10)N_2)[H_3As_3O_(10)]的水热合成与晶体结构

采用中温水热方法合成了新化合物(C2H10N2)[H3As3O10].利用X射线粉末衍射仪、红外光谱仪、热重分析仪及X射线单晶衍射仪表征了产物的结构.结果表明:该化合物属于单斜晶系,P2(1)/n空间群;晶胞参数为a=0.808 3(6)nm,b=1.446 9(9)nm,c=0.892 0(8)nm,β=98.16°,V=1.032 7(14)nm3,Z=4,F(000)=864,R1=0.025 3,wR2=0.093 4.其化学式为C2H13As3N2O10,分子量Mr=449.90.该化合物是由有机胺阳离子支撑的第一个具有一维链状结构的砷酸盐化合物,相邻的砷酸盐链通过AAAA堆积方式形成三维拓扑扩展结构.     

Hydrogen bonding and structure of Ba2Ru2Cl10O·10H2O

Dibarium μ‐oxido‐bis[pentachloridoruthenate(IV)] decahydrate, Ba₂Ru₂Cl₁₀O·10H₂O, has been prepared from ruthenium(III) chloride and barium chloride in hydrochloric acid. It crystallizes in the monoclinic system (space group C2/c). The structure consists of alternating layers of [Ru₂Cl₁₀O]⁴⁻ and [Ba(H₂O)₇]²⁺ complex ions along the a direction. The O atom bonded to ruthenium occupies the 4e site, with symmetry, while the other atoms occupy general 8f sites. The overall structure is held together by O—H...O hydrogen bonds and O—H...Cl dipole–dipole interactions.     

Interaction of closo-decaborate anion B10H 10 2− with iminium salts

The interaction of closo-decaborate anions with iminium salts, either formed in situ or introduced into the reaction as individual compounds, has been studied. The reaction leads to products with an exopolyhedral boron-nitrogen bond. The formation of compounds with exopolyhedral boron-chlorine and boron-carbon bonds is also possible. The crystal structures of [NMe₂(CH₂Cl)]₂B₁₀H₈ and 3-CH₃-2,8-[NMe₂(CH₂Cl)]₂-7-ClB₁₀H₆ have been studied.     

Mg2Ru2Cl10O·16H2O

Mg₂Ru₂Cl₁₀O·16H₂O {dimagnesium μ‐oxo‐bis­[penta­chloro­ruthenate(IV)] hexa­deca­hydrate} crystallizes in the monoclinic system (space group P2₁/c). The structure consists of layers of [Ru₂Cl₁₀O]⁴⁻ anions, [Mg(H₂O)₆]²⁺ cations and water mol­ecules stacked along the a axis. Only the O atom bonded to Ru occupies the 2a site with symmetry. All the other atoms occupy general 4e sites. The crystal structure is stabilized by O—H⋯O and O—H⋯Cl inter­actions.     

Monte Carlo simulation for pVT relationship of CO2+n-C4H10 and CO2+i-C4H10 systems

Monte Carlo simulation has been applied to calculate the pVT relationship of CO₂+butane (n-C₄H₁₀ and i-C₄H₁₀) systems at 310.93 K and up to 9.5 MPa. CO₂ is treated as a single-site molecule and butanes are treated as four-site molecules. The Lennard–Jones (12–6) potential is used as the site–site potentials and the combining rules proposed by Jorgensen et al. [W.L. Jorgensen, J.D. Madura, C.J. Swenson, J. Am. Chem. Soc. 106 (1984) 6638.] are adopted for unlike site pairs. The calculated results of the pVT relationship show good agreement with the experimental data [T. Tsuji, S. Honda, T. Hiaki, M. Hongo, J. Supercrit. Fluids 13 (1998) 15.] by introducing an intersite interaction parameter between unlike molecules. Furthermore, the radial distribution functions and the number of CO₂ and butanes around butanes are calculated as a fundamental information on the microscopic structures. It is found that the radial distribution functions and the number of CO₂ and n-C₄H₁₀ around n-C₄H₁₀ are different from those of CO₂ and i-C₄H₁₀ around i-C₄H₁₀.