Kinetics and mechanism of the cobaloxime(II) catalyzed oxidative dehydrogenation and double bond cleavage of 3,3',5,5'-tetra-tert-butyl-4,4'-dihydroxystilbene by O-2

被引:21
作者
Simandi, LI
Simandi, TL
机构
关键词
cobaloxime(II); oxidative dehydrogenation; oxidative cleavage; dihydroxystilbene cleavage; O-2; activation;
D O I
10.1016/S1381-1169(96)00269-5
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
In the presence of the cobaloxime(II) catalyst [Co(Hdmg)(2)(Ph(3)P)(2)], at room temperature and 1 atm O-2 or air, the dihydroxystilbene derivative referred to in the title (H(2)StQ) undergoes oxidative dehydrogenation to the corresponding stilbenequinone (StQ), and parallel oxidative cleavage at the C=C double bond to afford 2,6-di-tert-butyl-4-hydroxybenzaldehyde (Aid). The two products are formed via a common anion radical intermediate stable enough for detection by ESR spectroscopy. A detailed kinetic analysis has been carried out by volumetric, spectrophotometric and HPLC techniques. The observed kinetic behavior is consistent with the formation of a superoxocobaloxime(III) intermediate, which generates the free radical intermediate from H(2)StQ. In the steady state, the catalyst is present in a hydroxo-cobaloxime(III) precursor state, from which it is released via reduction to cobaloxime(II) by the anion radical.
引用
收藏
页码:299 / 309
页数:11
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