Tin(II) Halide Insertion or Halogen Exchange in the Reactions of Dihaloplatinum(II) Complexes with Tin(II) Halide

Reactions of SnCl₂ with the complexes cis‐[PtCl₂(P₂)] (P₂=dppf (1,1′‐bis(diphenylphosphino)ferrocene), dppp (1,3‐bis(diphenylphosphino)propane=1,1′‐(propane‐1,3‐diyl)bis[1,1‐diphenylphosphine]), dppb (1,4‐bis(diphenylphosphino)butane=1,1′‐(butane‐1,4‐diyl)bis[1,1‐diphenylphosphine]), and dpppe (1,5‐bis(diphenylphosphino)pentane=1,1′‐(pentane‐1,5‐diyl)bis[1,1‐diphenylphosphine])) resulted in the insertion of SnCl₂ into the Pt? Cl bond to afford the cis‐[PtCl(SnCl₃)(P₂)] complexes. However, the reaction of the complexes cis‐[PtCl₂(P₂)] (P₂=dppf, dppm (bis(diphenylphosphino)methane=1,1′‐methylenebis[1,1‐diphenylphosphine]), dppe (1,2‐bis(diphenylphosphino)ethane=1,1′‐(ethane‐1,2‐diyl)bis[1,1‐diphenylphosphine]), dppp, dppb, and dpppe; P=Ph₃P and (MeO)₃P) with SnX₂ (X=Br or I) resulted in the halogen exchange to yield the complexes [PtX₂(P₂)]. In contrast, treatment of cis‐[PtBr₂(dppm)] with SnBr₂ resulted in the insertion of SnBr₂ into the Pt? Br bond to form cis‐[Pt(SnBr₃)₂(dppm)], and this product was in equilibrium with the starting complex cis‐[PtBr₂(dppm)]. Moreover, the reaction of cis‐[PtCl₂(dppb)] with a mixture SnCl₂/SnI₂ in a 2 : 1 mol ratio resulted in the formation of cis‐[PtI₂(dppb)] as a consequence of the selective halogen‐exchange reaction. ³¹P‐NMR Data for all complexes are reported, and a correlation between the chemical shifts and the coupling constants was established for mono‐ and bis(trichlorostannyl)platinum complexes. The effect of the alkane chain length of the ligand and Sn^II halide is described.     

Synthesis, including asymmetric synthesis, of 1-substituted cyclopentenes from cyclobutanones with one-carbon ring-expansion by 1,2-carbon-carbon insertion of magnesium carbenoids

Treatment of 1-chlorovinyl p-tolyl sulfoxides, which were derived from cyclobutanones and chloromethyl p-tolyl sulfoxide, with lithium enolate of tert-butyl carboxylates, amides, lithium α-sulfonyl carbanions, and lithium α-carbanion of acetonitrile gave adducts in high to quantitative yields. The adducts were treated with Grignard regents, such as i-PrMgCl and EtMgCl in toluene to afford 1-substituted cyclopentenes in good to high yields with one-carbon ring-expansion via 1,2-carbon-carbon (1,2-CC) insertion reaction of the generated magnesium carbenoid intermediates. The magnesium carbenoid 1,2-CC insertion was found to be highly stereospecific. When optically pure chloromethyl p-tolyl sulfoxide was used in this procedure, optically active 1-substituted cyclopentenes were obtained in high optical purity.     

SYSTEM OF COINCIDENCE THEOREMS IN PRODUCT TOPOLOGICAL SPACES AND APPLICATIONS (Ⅰ)

A new notion of finite continuous topological space (in short, FC-space) with out convexity structure was introduced. A new continuous selection theorem was established in FC-spaces. By applying the continuous selection theorem, some new coincidence theorems for two families of set-valued mappings defined on product space of noncompact FC-spaces are proved under much weak assumptions. These results generalize many known results in recent literature. Some applications will be given in a follow-up paper.     

Stress Concentration at Interacting Spherical Inclusions in a Transversely Isotropic Body

An elastic-equilibrium problem is rigorously solved for a transversely isotropic body containing a finite number of arbitrarily arranged and oriented transversely isotropic spherical inclusions or an infinite periodic array of such inclusions. The solution is found based on the superposition principle for general solutions of single-particle problems and the addition theorems for partial vector solutions of the elastic equilibrium equations. The numerical results presented allow assessing the influence of matrix anisotropy on the stress concentration between inclusions     

Crystal structure and properties of a new mixed-valence compound LiMn2TeO6 and the survey of the LiMM′XO6 family (X = Sb or Te)

A new compound, LiMn²⁺Mn³⁺TeO₆, was prepared by solid-state reactions and characterized by powder X-ray diffraction, redox titration, conductivity, magnetic measurements and cycling behaviour in an electrochemical cell with Li counter electrode. It is triclinic, P1, a = 5.1077(1), b = 8.5707(1), c = 5.0589(1), α = 92.515(1)°, β = 92.092(2)°, γ = 89.818(2)°, Z = 2. The structure is based on strongly distorted hexagonal close packing of oxygen anions with cations occupying octahedral voids and represents the ordered variant of orthorhombic Li₂TiTeO₆ structure, derived from LiSbO₃. TeO₆ octahedra are almost regular but all four independent MnO₆ octahedra display severe distortions. Room-temperature conductivity is unexpectedly low for a mixed-valence compound, 2 × 10⁻⁷ S/cm. Together with the observed antiferromagnetic exchange interaction, this is a prerequisite for the colossal magnetoresistance effect. The unit cell volumes of LiMn₂TeO₆, LiSbO₃, Li₂M⁴⁺TeO₆ and LiMM′XO₆ series (a total of 21 compounds) correlate well with average cationic radii, but LiMn₂SbO₆ deviates considerably, and its preparation could not be reproduced.     

On finiteness and continuity of shot noise processes

For a rather general class of stochastic processes induced by time-stationary and by event-stationary random marked point processes, respectively, conditions are given for the almost sure finiteness of these processes and for their continuous dependence on the underlying random marked point process.     

锂离子电池硅基负极材料嵌锂行为的第一性原理研究

采用基于密度泛函理论的第一性原理平面波赝势方法,计算不同数量的锂离子引起的硅材料晶体结构的变化以及在嵌锂过程中形成Li_xSi(x=1、2、2.4、4.4)合金相的形成能与电子结构.采用LST/QST方法计算过渡态,模拟合金体相中的锂离子迁移过程.计算结果表明,随着嵌锂数量的增加,硅晶胞的体积在不断增大;Li_xSi合金相的形成能为负值,表明在嵌锂过程中锂离子和硅原子可以自发形成这些合金相,其中Li₇Si₃合金最容易形成;随着嵌锂量的增加,锂离子在费米能级处s轨道提供的电子数逐渐增加,锂硅合金在费米能级处的电子数量呈增大趋势,表明锂硅合金的导电性越来越优;常温下Li₂Si体相中很难直接形成锂离子空位,但锂离子空位的迁移过程很容易发生.