Concerted molecular decomposition of unsaturated and oxygen-containing compounds

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.