Transition state theory methyl radicals

In the following the salient features of the general transition state theory of Sections IIA and IIC, as applied to methyl radical recombination, are summarized, Details, where omitted, are given in Ref. 11c. 

Reaction of Ruthenium Carbonyls with Alkyl Radicals Boese and Goldman reported that in the presence of aryl ketones, d8 metal carbonyls such as Ru(CO)3(dmpe) mediate photocatalytic carbonylation of alkanes via a free radical mechanism.161 The activity was proposed to be initiated by the addition of an alkyl radical to the metal carbonyl and the formation of a metal-acyl radical intermediate. The transition states and the products of the reaction between alkyl radicals and ruthenium carbonyls were studied utilizing the B3LYP level of theory.162 The methyl addition to a carbonyl of Ru(CO)5 or Ru(CO)3(dmpe) was computed to be about 6 kcal/mol more exothermic than addition to free CO. 

CH3NC — CH3CN has also been carried out, the principal object being the interpretation of the transition state. This particular tautomerism has also been the subject of an investigation in which experiments have been made to assess the importance of radical chain effects in the thermally induced reaction. It is concluded that there is no reason to doubt the fact that the isomerization of methyl isocyanide is an excellent test for the theory of unimolecular reactions. 

The BDE theory does not explain all observed experimental results. Addition reactions are not adequately handled at all, mostly owing to steric and electronic effects in the transition state. Thus it is important to consider both the reactivities of the radical and the intended coreactant or environment in any attempt to predict the course of a radical reaction (31). Application of frontier molecular orbital theory may be more appropriate to explain certain reactions (32,33). Radical reactivities have been studied by esr spectroscopy (34-36) and modeling based on general reactivity and radical polarity (37). Recent radical trapping studies have provided considerable insight into the course of free-radical reactions, particularly addition polymerizations, using radical traps such as 2,4-diphenyl-4-methyl-l-pentene (a-methylstyrene dimer, MSD) (38-44) and 1,1,3,3-tetramethyl-2,3-dihydro-liT-isoindol-2-yloxyl (45-49). 

Wardlaw DM, Marcus RA (1986) Unimolecular reaction-rate theory for transition-states of any looseness. 3. Application to methyl radical recombination. J Phys Chem 90 5383-5393... 

Recombination of alkyl radicals, as that of atoms, occurs practically without an activation energy. In the gas phase at a sufficiently high pressure the recombination of methyl radicals is bimolecular with the rate constant close to (l/4)Zo (where Zo is the frequency factor of bimolecular collisions, and the factor 1/4 reflects the probability of collisions of particles with the antiparallel orientation of s ins). The theoretical estimation of the constant at a collision diameter of 3.5-10 m agrees with the experimental value = 2-10 ° l/(mol-s) (300 K). This k value agrees with the estimation by the theory of absolute reaction rates under the assumption that the free rotation of methyl groups is retained in the transition state. In the liquid the recombination of meth)d radicals is bimolecular with the rate constant of difiiision collisions (see Qiapter 5). For example, in water 2k = 3.2-10 l/(mol s) (298 K). Ethyl radicals react with each other by two methods recombine and disproportionate... 

In the literature there is only one serious attempt to develop a detailed mechanistic model of free radical polymerization at high conversions (l. > ) This model after Cardenas and 0 Driscoll is discussed in some detail pointing out its important limitations. The present authors then describe the development of a semi-empirical model based on the free volume theory and show that this model adequately accounts for chain entanglements and glassy-state transition in bulk and solution polymerization of methyl methacrylate over wide ranges of temperature and solvent concentration. 

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