Concerted molecular decomposition of unsaturated and oxygen-containing compounds

被引:11
作者
Denisov, E. T. [1 ]
Pokidova, T. S. [1 ]
机构
[1] Russian Acad Sci, Inst Problems Chem Phys, Chernogolovka 142432, Moscow Region, Russia
关键词
GAS-PHASE PYROLYSIS; THERMAL-DECOMPOSITION; TRANSITION-STATE; VINYL ETHERS; TERT-BUTYL; THERMOLYTIC REACTIONS; BETA-SUBSTITUENTS; ESTER PYROLYSIS; RELATIVE RATES; MECHANISM;
D O I
10.1070/RC2012v081n05ABEH4221
中图分类号
O6 [化学];
学科分类号
0703 ;
摘要
Kinetic data on concerted molecular decomposition of alkenes, alcohols, ethers and esters, unsaturated acids and nitro compounds are summarized and analyzed. Experimental data are analyzed within the framework of semiempirical models treating the decomposition as (i) one-centre reaction involving transfer of hydrogen atom and (ii) two-centre reaction with simultaneous H atom transfer and cleavage of C-C, C-O or C-N bond. The effects of the molecular geometry of compounds and other factors on the activation energy of decomposition are discussed. The results of calculations of the spectrum of activation energy for concerted decomposition and the results of quantum chemical calculations of the transition-state geometries and energy characteristics are presented. The bibliography includes 59 references.
引用
收藏
页码:415 / 434
页数:20
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