A Generalized Unpaired Electron Spin Density Equation and Organic Hyperconjugation Mechanism

A large class of stereochemcial and related interactions in organic chemistry are repulsive and others are attractive, but the relative orientation of two methyl groups and the amount of energy required to twist one relative to the other (the hindered rotation energy barriers), or the alignment of such a group with respect to a conjugated ring to which it is attached (widely attributed to a mechanism called “hyperconjugation”) are estimated to be small in compared with the total energy of the molecule. We used theories of both isotropic and anisotropic proton hyperfine interactions in the π‐electron systems developed in the early sixties. They are approximated by the magnetic dipole nteractions between each proton and an electron spin magnetization that is distributed in 2s and 2p Slater atomic orbitals center on carbon atoms. We have extended these theories to the non‐planar olefinic cation radicals, which are very important in biochemistry as well as in petroleum catalysis. A three dimensional electron spin density equation has been developed in this paper to handle some Jahn‐Teller vibronic molecules. The new electron spin density equation related the observed proton hyperfine splittings to the non‐planar structures of the open‐chain alkene cation radicals generated by radiolysis and various chemical oxidation methods. The spin densities and the conformational calculations based on valence bond theory and symmetry principles are compared with some more elaborated molecular orbital calculations in the literature. The localized valence bond approaches are better in accord with our experimental results. The anomalous line‐width effect of the four methyl groups observed in the 2,3‐dimethyl‐2‐butene cation radicals also confirmed the positive sign of the electron‐proton hyperfine constant of hyper‐conjugation mechanism. A methyl substituent attached to a conjugated molecule often behaves as if it formed part of the region of conjugation; the charge appears to flow from the methyl group into the π electron system and it may also give rise to an appreciable dipole moment. Methylation also gives rise to an appreciable dipole moment, and the resultant red shift of electronic absorption bands is of some importance in the design of dye molecules.     

Zig‐Zag Diphosphene Oligomers Linked by Silver(I) Cation

The coordination of silver cation to diphosphene Mes*P=PMes* ( 1 , Mes* = ^tBu₃C₆H₂) was investigated in detail. The reaction of 1 with Ag[Al(OR_F)₄] (OR_F = OC(CF₃)₃) in the ratios of 2 : 1, 3 : 2 and 1 : 2 led to the formation of the first cationic silver linked diphosphene complexes 2 — 4 . Complexes 2 and 3 contain two and three diphosphene molecules linked by the linear Ag(I) cation, respectively, and they feature unusual zig‐zag topologies. Complex 4 is a dinuclear silver complex, and each Ag(I) center features a tetrahedral geometry, coordinated by one phosphorus atom of diphosphene 1 and three chloro atoms of two CH₂Cl₂ molecules.     

Effect of solvent on the cation-sensitive fluorescence of polyanions bearing 4′-acryloylbenzo-18-crown-6 Units

Changes in the fluorescence intensity of polyanions bearing 4-acryloylbenzo-18-crown-6 units on the addition of cations were studied in a mixed solvent of methanol and water at 30°C. The sensitivity of the change in fluorescence intensities of the polymers toward cations was strongly enhanced compared to that of the corresponding model compound. When alkali metal cations were added, the fluorescence intensity of the polymers decreased in the orders Li⁺>Na⁺>Cs⁺>Rb⁺>K⁺ in a methanol-water (19) mixture and Li⁺>Na⁺>Rb⁺>K⁺Cs⁺ in a methanol-water (91) mixture. Alkaline earth metal cations and alkylamine hydrochlorides decreased the fluorescence intensity of the polymers in a methanol-water (19) mixture. The cation-dependent decrease in the fluorescence intensity of the polymers was affected by the water fraction in a mixed solvent of methanol and water.     

A reinvestigation of quaternary layered bismuth oxyhalides of the Sillén X1 type

A family of layered bismuth oxyhalides, L^I_0.5Bi_1.5O₂X and L^IIBiO₂X has been reinvestigated. Formation of X1-type Sillén compounds has been established for L^I=Li, Na, L^II=Ca, Sr, Ba, and X=Cl, Br, I, but the details of their crystal structures are different. While all L^I_0.5Bi_1.5O₂X, CaBiO₂Br, and CaBiO₂I adopt the disordered tetragonal Nd₂O₂Te structure, all compounds of L^II=Sr and Ba are orthorhombic and isostructural to PbSbO₂Cl, due to L/Bi cation ordering. Crystal structures have been determined for CaBiO₂I, SrBiO₂Br, SrBiO₂I, and BaBiO₂I. We discuss the factors which determine the occurrence and type of cation ordering in the quaternary bismuth and antimony X1-type oxyhalides. We also predict that more isostructural compounds can be prepared with antimony.     

聚（甲基丙烯酸甲酯—二甲基二烯丙基氯化铵）的合成及表征

以水和乙醇作混合溶剂，用逐步滴加甲基丙烯酸甲酯的方法，通过自由基聚合，由溶解性和共聚活性差异较大的两种单体ＭＭＡ和二甲基二烯丙基氯化铵合成了新型含阳离子共聚物聚，并用ＩＲ和＾１Ｈ－ＮＭＲ进行了分析表征。该共聚物溶于丙酮和水组成的二元溶剂，并与Ｐ（ＭＭＡ－ＭＡＡ）有较强的分子复合能力。     

Ti4+修饰阳离子交换树脂催化制备环已烯

在Ti^4 修饰阳离子交换树脂催化剂上进行了环己醇脱水制备环己烯的反应，考察了催化剂吸附毗啶的FT-IR，证实了该催化剂表面具有Bronsted酸和Lewis酸性住是催化环己烯脱水反应的物质基础，实验结果表明：修饰树脂具有较高的热稳定性，Ti^4 交换容量对阳离子交换树脂的催化活性存在着明显的影响，催化剂对环己醇脱水制环己烯反应的活性高，并得到该反应的优化条件如下：环己醇40g，催化剂5g，反应温度175℃，反应时问60min，在此条件下，环己烯的产率达89％。     

Magnetism and structural chemistry of the n=2 Ruddlesden-Popper phase La3LiMnO7

Polycrystalline samples of the n=2 Ruddlesden-Popper phase La₃LiMnO₇ have been prepared and characterized. X-ray and neutron diffraction suggest that the structure is tetragonal with a disordered distribution of Li and Mn cations over the octahedral sites, but ⁶Li MAS NMR shows that the Li and Mn are 1:1 ordered locally. Electron microscopy shows that the stacking of the cation-ordered, perovskite-like bilayers along the crystallographic z-axis is disordered on the distance scale sampled by X-ray and neutron diffraction. Magnetometry data and neutron diffraction data collected at 2 K together suggest that the Mn cations within each structural domain order antiferromagnetically at 14 K, but that the disorder along z prevents the establishment of long-range magnetic order.     

Crystal structures and phase transition in the system SrTiO3-La2/3TiO3

The distribution of A-site cations in the perovskite system La_xSr_1−3x/2TiO₃ depends on the concentration of La³⁺ ions and associated vacancies. For small x (x?0.2), the substitutions are expected to be random. For x?0.55, the cations are ordered in such a way that successive layers of A-sites are occupied to greater and lesser degree, and this ordering drives a tetragonal distortion. For x from about 0.3 to 0.5, the X-ray patterns show diffuse peaks indicative of similar ordering, but this is not long-range order and no tetragonal distortion results. The lower temperature structures also exhibit out-of-phase tilting of the TiO₆ octahedra, setting in at temperatures varying linearly with composition from 105 K for x=0, to about 650 K at x=2/3.     

A model for cation adsorption to clays and membranes

A cation adsorption model is presented and its recent applications are discussed. The model combines electrostatic equations with specific binding, and considers neutral and positively charged complexes between the negative surface sites and organic cations in a closed system. Extensions in the model account for dye aggregation in solution, and for the formation of solution complexes of inorganic cations, such as [M⁺⁺ Cl^–]⁺. The amounts of 45Ca²⁺ adsorbed to vesicles extracted from the plasma membranes of melon root cells could be adequately simulated and predicted. The binding coefficients determined for Ca²⁺, Na⁺, and Mg²⁺ are in the range of values previously deduced for binding to phospholipid components. Model calculations were applied to the test of hypotheses on the effect of salt stress on the growth of roots. The adsorption of monovalent organic cations to montmorillonite is characterized by binding coefficients that are at least six orders of magnitude larger than those of Na⁺, Mg²⁺, Ca²⁺, and Cd²⁺, or those of CdCl⁺ or CaCl⁺. Monovalent organic cations were found to adsorb 140–200% of the cation exchange capacity of the clay and to cause charge reversal. Deductions from adsorption results of acriflavin are consistent with those drawn from the application of other experimental methods. Preliminary results on the adsorption of divalent organic cations are presented. Agro-environmental applications of organo-clays are discussed.