Mass spectral studies of some π-benzoylcyclopentadienylmanganese tricarbonyl derivatives

The loss of three CO groups from derivatives of π-C₆H₅COC₅H₄Mn(CO)₃ is a two-step mechanism in which the loss of two CO groups is followed by a third. Subsequent fragmentations generally involve rearrangement processes which often result in ring closure within the organic substrate. The central metal atoms plays an important part in such rearrangement processes and the positive charge can reside either on the metal or the ligand depending on the nature of the ligand. Fragmentation patterns are proposed for these systems.     

pH滴定-主成分回归法同时测定酚类同系物

本文利用pH滴定－主成分回归法同时测定了苯酚、邻苯二酚、邻苯三酚的混合物，结果良好。通过交差验证法，本文还对采样区间和采样间隔作了详细讨论。     

Kinetics of the grignard reaction with silanes in diethyl ether and ether-toluene mixtures

Kinetics of the reactions of butylmagnesium chloride and phenylmagnesium bromide with tetraethoxysilane and methyltrichlorosilane was investigated in diethyl ether and diethyl ether-toluene mixtures. Replacement of ether by toluene significantly accelerates the reaction with alkoxysilanes, while no effect was found for the reaction with chlorosilanes. We established that the reaction with alkoxysilanes consists of replacement of a donor molecule at the magnesium center by the silane followed by subsequent rearrangement of the complex to products through a four-center transition state. Chlorosilanes react differently without solvent molecule replacement but also via a four-center transition state. Large negative activation entropies are consistent with formation of cyclic transition states. Small activation enthalpy values together with remarkable exothermicity point to early transition states of the reactions.     

Regioselective synthesis of the bridged tricyclic core of Garcinia natural products via intramolecular aryl acrylate cycloadditions

[reaction: see text] Two different routes to the tricyclic core of Garcinia-derived natural products are described. The first approach is based on a tandem Claisen/Diels-Alder rearrangement and delivers the desired lactone 14. The second approach, employing a Wessely oxidation/Diels-Alder protocol, leads to the same caged heterocycle, albeit with modified constitution.     

Linear response time-dependent density functional theory for van der Waals coefficients

A linear response time-dependent density functional theory is described and used to calculate the dynamic polarizabilities and van der Waals C(6) coefficients of complex atom pairs. We present values of C(6) for dimers of main group atoms and the first row of transition metal atoms.     

Convenient syntheses of "heavy fluorous" cyclopentadienes and cyclopentadienyl complexes with three to five ponytails

Reactions of (eta5-C5H(5-x)Brx)M(CO)3(M = Re, Mn; x= 1, 3, 4, 5) and IZn(CH2)2R(f8) in the presence of Cl2PdL2 catalysts give the title complexes (eta5)-C5H(5-x)(CH2)2R(f8)x)M(CO3), accompanied in the case of x= 5 by hydride-transfer byproducts. Extremely high fluorophilicities are realized, and the cyclopentadienyl ligands are readily detached (hnu) from the manganese complexes.     

大黄素的吸附溶出伏安研究

研究了大黄素在甲醇、二氧六环和水的混合溶剂中以１％硼砂为支持电解质在静汞电极上的吸附伏安行为。建立了用微分脉冲吸附溶出伏安法测定其含量的新方法。在－０３０Ｖ（ｖｓＡｇ／ＡｇＣｌ）电位下吸附富集，可得一灵敏的还原溶出峰，峰电位－０７５Ｖ，浓度在５×１０－８～５×１０－９ｍｏｌ／Ｌ范围内与峰电流具有良好的线性关系，最低检出限为１×１０－９ｍｏｌ／Ｌ。该法用于含有大黄素体系的测定简便、快速、可靠。     

Comparison between the symmetry-correlation examination and the perturbation method

A comparison between the construction of symmetry-correlation diagrams and the perturbation method for studying chemical reactions is carried out. The perturbation method consists of decomposing the system Hamiltonian H into a sum, H = H₀ + H′. Various symmetry correlation schemes appearing in the literature may be explained by the nonuniqueness of the decomposition scheme. All symmetry selection rules may be viewed as the varieties. By examining the symmetry-correlation diagrams, processes under investigation may be called “forbidden” or “allowed,” depending on the topological feature. Of particular importance is the topology associated with the “avoided crossing.” By making the comparison, we can establish the correspondence of the two methods and conclude that the perturbation order furnishes the origin of the “forbiddenness” of a process.