KINETICS AND MECHANISM OF THE REACTION BETWEEN CHROMIUM(II) AND 1,2-BIS(2-PYRIDYL)ETHYLENE IN ACIDIC AQUEOUS-SOLUTIONS

被引：6
作者：
PETROU, AL
机构：
来源：
JOURNAL OF THE CHEMICAL SOCIETY-DALTON TRANSACTIONS | 1993年 / 24期
关键词：
D O I：
10.1039/dt9930003771
中图分类号：
O61 [无机化学];
学科分类号：
070301 ; 081704 ;
摘要：
The reduction of 1,2-bis(2-pyridyl)ethylene by chromium(II) perchlorate in aqueous perchloric acid to the corresponding dipyridylethane has been shown to take place through a sigma-bonded organochromium intermediate. The acidolysis of this complex takes place in two stages, the first of which has an observed rate constant k(obs) = k0 + k1[H+]. The corresponding activation parameters are DELTAH-0 double-dagger = 92.0 =/- 1.6 kJ mol-1, DELTAS0 double-dagger = -15.1 +/- 4.9 J K-1 mol-1, DELTAH-1 double-dagger = 142 +/- 3 kJ mol-1, and DELTAS1 double-dagger = 142 +/- 7 J K-1 mol-1. The experimental results are discussed in terms of the nature of the lowest unoccupied molecular orbital of the substrate, which is 'ethylenic'.
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页码：3771 / 3775
页数：5
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