Synthesis and transformations of metallacycles. 30. Aluminacyclopentanes in the synthesis of secondary and tertiary alcohols

A method for the synthesis of secondary and tertiary alcohols was developed. The method is based on cycloalumination of olefins with trialkylalanes in the presence of Zr-containing catalysts followed by the CuCl-catalyzed in situ reaction of the corresponding aluminacyclopentanes with aldehydes or ketones.     

Fe(III)与2,3-二羟基苯磺酸钠配位反应的动力学研究

[H+]在0.01～0.70mol?L-1范围内,离子强度为1.00mol?L-1,[Fe(III)]>>[配体]、[H+]>>[配体]的条件下,研究了Fe(III)与2,3-二羟基苯磺酸钠(Tiron)的配位反应.发现当[H+]≤3.00×10-2mol?L-1时,[Fe(III)]2对反应速率有明显的贡献.求得了相关反应的动力学参数,从而揭示了FeOH2+和FeOH24+与Tiron配位的解离反应途径及FeOH32+的缔合反应机制,并提出了该配位反应的可能机理.     

双甘肽稀土配合物溶液结构的13C和1H NMR研究

~(13)C and ~1H NMR technique was used to study the interaction of Gly-Gly with heavy lanthanide cations Dy~(3+), Ho~(3+), Er~(3+), Tm~(3+) and Yb~(3+) in aqueous solution. The stability constants for the 1:1 and 1:2 complexes of Gly-Gly with Ho~(3+) and Yb~(3+) were determined from the titration curves of chemical shift versus concentration ratio of lanthanide to Gly-Gly. The solution structure of the Ln-Gly-Gly complex was analyzed based upon the ~(13)C and ~1H lanthanide-induced shifts and the results show that in the complex Gly-Gly is coordinated to the lanthanide ion through the carboxyl oxygens with the backbone of the ligand in an extended state.     

Oxidation of thiol compounds by molecular oxygen in aqueous solutions

Side self-oxidation of thiols was studied. It was found that these reactions in neutral and alkaline solutions are induced by impurities of variable-valence metals. The ability of transition metals to catalyze oxidation of thiols changes in the order Cu > Mn > Fe > Ni Co. The plot of the self-oxidation rate vs. pH passes through a maximum whose position on the pH scale depends on both the nature of metal and the structure of the thiol oxidized. For thiols having different structures, the kinetic orders in reactions catalyzed by copper ions differently vary with pH, which is apparently associated with the formation of complexes possessing different catalytic activity.     

Oxovanadium(V)-catalyzed enantioselective Meerwein-Ponndorf-Verley cyanation of aldehydes using acetone cyanohydrin

Oxovanadium(V)(salen) complex 4 was found to catalyze Meerwein-Ponndorf-Verley cyanation of aliphatic aldehydes with good to high enantioselectivity. This cyanation showed a positive nonlinear effect.     

MCM-41-supported bidentate phosphine palladium(0) complex: a highly active and recyclable catalyst for the Sonogashira reaction of aryl iodides

The first MCM-41-supported bidentate phosphine palladium(0) complex has been prepared. This complex is a highly efficient catalyst for Sonogashira reaction and can be reused at least 10 times without any decrease in activity.     

SYNTHESIS AND CATALYTIC PROPERTY OF POLYSTYRENE SUPPORTED GLUTAMIC ACID SCHIFF BASE COMPLEX OF Mn（ Ⅱ ） IN AEROBIC OXIDATION OF CYCLOHEXENE

The polystyrene supported glutamic acid Schiff base complex of Mn （ Ⅱ ） （PS-Sal-Glue-Mn） was prepared with chloromethylated styrene polymer beads, 2,4-dihydroxybenzaldehyde, L-glutamic acid and manganese （ Ⅱ ） acetate tetrahyrate. The polymeric ligand and the complex were characterized by FT-IR, small area X-ray photoelectron spectroscopy （XPS） and 1CP-AES. In the presence of the manganese complex, cyclohexene （1） was effectively oxidized by molecular oxygen without reductant. The major products of the reaction were 2-cyclohexen-l-ol （2）, 2-cyclohexen-l-one （3） and 2-cyclohexen-1- hydroperoxide （4）, which was different with typical oxidation of cyclohexene. The influence of reaction temperature and additive for oxidation had been studied. The selectivity of 2-cyclohexen-1-hydroperoxide varied with reaction time and different additives. The mechanism of cyclohexene oxidation had also been discussed.     

在配位体络合体系中合成窄分布聚苯乙烯

本文报道了在RLi-配位体络合体系中阴离子聚合方法合成窄分布聚苯乙烯的研究结果.在己烷、庚烷、甲苯等溶液中合成分子量范围为10~2～10~3。的窄分布聚苯乙烯(MWD<1.10)时,以鹰爪豆矸、N,N,N’,N’-四甲基乙二胺为配位体的络合体系,聚合操作简便,效果非常好.在非极性溶剂中加一定比例的THF以后,该体系也能合成分子量范围为10~4～10~5的窄分布聚苯乙烯.     

The Inclusion Mode of tert-Butylbenzene in the 1-D Channel of Microporous β-Bis(1,1,1-trifluoro-5, 5-dimethyl-5-methoxy-acetylacetonato) copper(II)

Inclusion of tert-butylbenzeneinto the l-D channel of the titlehost matrix results in a-[CuL₂]1/3(tert-butylbenzene)inclusion compound(trigonal, space groupR =3;a = 24.495(3),c = 10.510(2) Å,V = 5461(1) ų,Z = 9;R = 0.049). The observed guest–host mole ratio of 1/3 was confirmed by X-ray diffraction and arises from the stoichiometric filling of the larger wide segments of the channel. This contrasts with the benzene inclusion compound studied previously, where both the larger and smaller wide segments were occupied to give a 2/3 guest–host stoichiometry. A comparison of these two structures explains the experimental fact that the guest–host mole ratios for inclusions of the title host lie between values of 1/3 and 2/3for 20 different benzene derivatives.     

Size of Micelles Determined by Static Fluorescence Quenching

We developed a new method to measure the average aggregation number of large rod-like micelles using static fluorescence self-quenching of a solubilized fluorophore. The method is based on the increase of self-quenching of micelle-solubilized pyrene through excimer formation. We consider the effect of random distribution of pyrene in micelles and the micellar size distribution. The measured average aggregation <n> _M is based on a new M-weighted raging similar to our exponential-weighted averaging in the transient decay method. We apply this method to study the effect of a large concentration of salt on the average aggregation behavior of sodium dodecyl sulfate (SDS) and cetyle tetraammonium bromide (CTAB). The sizes increase with increasing ionic concentrations. For SDS, we used the thermodynamic model developed by Missel et al. to calculate < n > _M which we compare with experimental results.