Solvent cages reactions

Once the radicals diffuse out of the solvent cage, reaction with monomer is the most probable reaction in bulk polymerizations, since monomers are the species most likely to be encountered. Reaction with polymer radicals or initiator molecules cannot be ruled out, but these are less important because of the lower concentration of the latter species. In the presence of solvent, reactions between the initiator radical and the solvent may effectively compete with polymer initiation. This depends very much on the specific chemicals involved. For example, carbon tetrachloride is quite reactive toward radicals because of the resonance stabilization of the solvent radical produced [1] ... 

A choice between the conventional (or classical) and ion-radical mechanism is a very important issue. The ion-radical pathway leads to products of the desired structure, makes the conversion conditions milder, or changes the reactivity of the secondary intermediate particles. If ion-radicals form and react in a solvent cage, reaction proceeds rapidly, product... 

Both radical reaction products are believed to be solvent cage reactions for the following reasons ... 

In a bimolecular reaction in solution reactants diffuse through the assembly of solute and solvent molecules (Scheme 1) and collide to form an encounter complex within a solvent cage. Reaction is not possible until any necessary changes occur in the ionic atmosphere to form an active complex and in solvation (such as desolvation of lone pairs) to form a reaction complex in which bonding changes take place. The encounter complex remains essentially intact for the time period of several collisions because of the protecting effect of the solvent surrounding the molecules once they have collided. The products of the subsequent reaction could either return to reactants or diffuse into the bulk solvent. 

As demonstrated by various reactions in the field of organic chemistry, it is often not easy to distinguish route i) from ii). The radical type SET mechanism may proceed as solvent-caged reaction, and as such it may show very similar... 

Hydrocarbon autoxidation takes place via a complex set of radical reactions, some of which were only recently identified. One of the mechanistic difficulties is that the reactions can only be indirectly investigated by monitoring the evolution of stable products. The input of quantum-chemical calculations, in combination with theoretical kinetics, turned out to be a crucial tool to construct a generic mechanism. One of the new insights is the importance of the copropagation of the primary hydroperoxide product. A solvent-cage reaction, activated by the exother-micity of this secondary step, leads to the formation of the desired alcohol and... 

Solvation energy 29 Solvent cage reactions, in nitrous acid deaminations 471 Solvent effect, in ozonolysis 336 Sommelet-Hauser rearrangement 420-423... 

Path (/) solvent cage reactions. From the stereochemical results discussed, it is apparent that the deamination of secondary carbin-amines does not involve, to any extent, free carbonium ions, or the attack of solvent on a reaction intermediate. Front-side exchange accounts for only a part of the solvent incorporation in acetic acid. By analogy to the nitrosoamide reaction, and from results such as those shown in equation (152) it is proposed that the remainder of... 

The introductory remarks about unimolecular reactions apply equivalently to bunolecular reactions in condensed phase. An essential additional phenomenon is the effect the solvent has on the rate of approach of reactants and the lifetime of the collision complex. In a dense fluid the rate of approach evidently is detennined by the mutual difhision coefficient of reactants under the given physical conditions. Once reactants have met, they are temporarily trapped in a solvent cage until they either difhisively separate again or react. It is conmron to refer to the pair of reactants trapped in the solvent cage as an encounter complex. If the unimolecular reaction of this encounter complex is much faster than diffiisive separation i.e., if the effective reaction barrier is sufficiently small or negligible, tlie rate of the overall bimolecular reaction is difhision controlled. 

For very fast reactions, the competition between geminate recombmation of a pair of initially fomied reactants and its escape from the connnon solvent cage is an important phenomenon in condensed-phase kinetics that has received considerable attention botli theoretically and experimentally. An extremely well studied example is the... 

In discussing mechanism (5.F) in the last chapter we noted that the entrapment of two reactive species in the same solvent cage may be considered a transition state in the reaction of these species. Reactions such as the thermal homolysis of peroxides and azo compounds result in the formation of two radicals already trapped together in a cage that promotes direct recombination, as with the 2-cyanopropyl radicals from 2,2 -azobisisobutyronitrile (AIBN),... 

The assumption that k values are constant over the entire duration of the reaction breaks down for termination reactions in bulk polymerizations. Here, as in Sec. 5.2, we can consider the termination process—whether by combination or disproportionation to depend on the rates at which polymer molecules can diffuse into (characterized by kj) or out of (characterized by k ) the same solvent cage and the rate at which chemical reaction between them (characterized by kj.) occurs in that cage. In Chap. 5 we saw that two limiting cases of Eq. (5.8) could be readily identified ... 

Evidence that the actual methylation of the anion can be divided into SnI, Eq. (3), and Sx2 types, Eq, (4), is provided by a whole series of investigations. " The terms S l and 8 2 must be taken to mean reactions with, respectively less or greater nucleophilic participation of the anion in the transition state. The importance of oriented ion pairs" in the solvents of low polarity frequently used in reactions involving diazomethanc, e.g., the ions formed by a diazoalkane and benzoic acid in ether, should be emphasized. The expression oriented ion pair means that, because of insufficient solvation, the ions are not individually solvated but exist as ion pairs within a solvent cage. The orientation within the ion pair is defined electrostatically, and this orientation fixes the path for the productdetermining step. Several indications (cf, foo otes 22-24) in the literature indicate the occurrence of carbonium ions and oriented ion pairs in Broensted-type equilibria of the type of Eq. (2). 

In other cases, the cage reaction may simply lead to reformation of the initiator. This process is known as cage return and is important during the decomposition of BPO (Section 3.3.2.1.1) and DTBP (Section 3.3.2.4). Cage return lowers the rate of radical generation but does not directly yield byproducts. It is one factor contributing to the solvent and viscosity dependence of kA and can lead to a reduced at high conversion. 

The proportion of useful radicals generated from common dialkyldiazenes is never quantitative typically it is the range 50-70% in media of low viscosity i.e. in low conversion polymerizations).3 88 89 The main cause of this inefficiency is loss of radicals through self-reaction within the solvent cage. 

While the rate of azo-compound decomposition shows only a small dependence on solvent viscosity, the amount of cage reaction (and hence f) varies dramatically with the viscosity of the reaction medium and hence with factors that determine the viscosity (conversion, temperature, solvent, etc.) 1... 

The other mechanism which has been advocated58 is that known as the radical-pair mechanism , in which two cation radicals are thought of as intermediates held in a solvent cage so preserving the intramolecularity of the reaction, viz. 

Collisions in the gas phase, whether they result in a reaction or not, are timed somewhat uniformly. In solutions, however, solute pairs undergo multiple collisions within a solvent cage. Once two solute species are in one cage, they are likely to remain neighbors for some time, during which they experience repeated collisions. 

Rate constants that are near the diffusion-controlled limit may need to have a correction applied, if they are to be compared with others that are slower. To see this, consider a two-step scheme. In the first, diffusion together and apart occur the second step is the unimolecular reaction within the solvent cage. We represent this as... 

FIGURE 5.3. A schematic free-energy profile for a reference reaction in a solvent cage. 

With these AG we can estimate the energetics of the key asymptotic point on the potential surface of the reference reaction in which AH and R-O-R are kept in the same solvent cage. First, we note that (AG2) is... 

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