Kinetic Studies of Substitution Reactions of Uranyl(VI) Schiff Base Complexes with Tributylphosphine

被引:1
|
作者
Asadi, Zahra [1 ]
Shorkaei, Mohammad Ranjkesh [1 ]
机构
[1] Shiraz Univ, Dept Chem, Coll Sci, Shiraz, Iran
关键词
STRUCTURAL-CHARACTERIZATION; DIMETHYL-SULFOXIDE; N; N-DIMETHYLFORMAMIDE; REACTIVITY;
D O I
10.1002/kin.20753
中图分类号
O64 [物理化学(理论化学)、化学物理学];
学科分类号
070304 ; 081704 ;
摘要
The kinetics of the substitution reaction of uranyl Schiff base complexes with tributylphosphine was studied spectrophotometrically in acetonitrile. Uranyl complexes have a pentagonal bipyramidal structure with a trans-UO2 moiety at the axial positions. In uranyl tetradentate Schiff base complexes, the fifth position of the equatorial plane is occupied by the solvent molecule, which weakly coordinates to the U center. In a substitution reaction, tributylphosphine can easily replace the solvent molecule. By considering the excellent linearity of kobs versus the molar concentration of tributylphosphine, the large negative values of ? S#, and the small values of ? H#, an associative (A) mechanism has been suggested. By comparing the rate constants (k2) and the activation parameters, it is obvious that two parameters are effective in the rate of substitution reactions; The first parameter is the steric effect that the rate of reaction has been decreased by increasing this factor, and the other parameter is the electronic property that the electron-withdrawing group leads to increase the rate of reaction and the electron donor group decreases it. (C) 2013 Wiley Periodicals, Inc. Int J Chem Kinet 45: 168174, 2013
引用
收藏
页码:168 / 174
页数:7
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