Thermal decomposition computational studies

Akasaka, Effect of substituents on the thermal decomposition of diazirines experimental and computational studies, J. Org. Chem., 2003, 68, 7471-7478. 

Three further computational explorations of carbene reaction mechanisms have been reported. DFT study of the Reimer-Tiemann reaction (formal reaction between CCl2 and a phenoxide ion) using either potassium or sodium hydroxide as base has revealed that the active carbenic species is an alkaline carbenoid form rather than its free form as suggested earlier. DFT study of the reaction of CHF with dioxygen has confirmed fhaf fhe firsf step involves formation of the planar HFCO2 adduct. The initial steps of 2,5-dimethylfuran thermal decomposition have been computationally identified as scission of the C—H bond in the methyl side chain and subsequent formation of ft- and a-carbenes (39) and (40) via [3,2]-H and [2,3]-methyl shifts, respectively (Scheme 6). Once generated, carbenes (39) and (40) are believed to follow diverse fragmentation pathways. ... 

Sorescu et al. have published theoretical and computational studies of energetic salts [22]. Opinions concerning the mechanism of thermal decomposition of nitrates are approximately the same in both monographs. The decomposition mechanism of the best-known oxidizer, ammonium nitrate (AN), is given below. In the solid state, AN is dissociated according to the following equilibrium [ 11,22] ... 

ParkJ, Xu ZF, Lin MC. Thermal decomposition of ethanol. II. A computational study of the kinetics and mechanism for the H+C2H5OH reaction. / Chem P/iys. June 2003 118 9990-9996. 

A wealth of experimental data on the thermal dioxetane decomposition and the excited-state generation in the thermolysis process has been comprehensively surveyed in previous reviews". During the last decade, computational elucidation of the thermal cleavage received major attention and in the present subsection we consider the relevant studies. Computations on the dioxetane thermolysis were conducted by both ab initio24 and semiempirical25 methods at different levels of sophistication. 

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