Fragmentation radical decay

The fragment radical of 43 amu from acetone, the acetyl intermediate, builds up in 60 fs and decays in 420 fs. The first a-cleavage takes place in a time comparable to the vibrational period of the C—C bond, 43 fs, while the second is much slower. The intermediate of 46 amu from acetone-dg rises in 80 fs and decays in 670 fs. 

These high-excited-state molecules can follow a number of paths. They can emit radiation, fragment into ions or radicals, decay to lower excited states by internal conversion, or finally return to the ground state (Reactions [8.8]-[8.11]) ... 

Polyfunctional monomers have been put to use in the crosslinking rf polypropylene and of branched polyalkenes where polymer radicals decay in disproportionatum reaction or fragmentate preferentially. 

Content of prime - tertiary peroxide groups was measured by the quantity of products of complete decay, which were measured by chromatography. It is known that the main contents in products of the complete decay of Oct-MA-TBPMM samples are acetone and 2,2-dimethylpropanol, which arise in reactions of chain fragmentation of tert-butylperoxy radical or in reaction of chain transfer of this radical. In this case the sum of acetone and 2,2-dimethylpropanol molecules is equal to the quantity of peroxide groups in polymer. As an internal standard we used chloroform. 

Watanabe et al,25-5 52s applied AMS dimer (116) as a radical trap to examine the reactions of oxygen-centered radicals (e.g. r-butoxy, cumyloxy, benzoyloxy). AMS dimer (116) is an addition fragmentation chain transfer agent (see 6.2.3.4) and reacts as shown in Scheme 3,96. The reaction products are macromonomers and may potentially react further. The reactivity of oxygen centered radicals towards 116 appears to be similar to that of S.2 1 Cumyl radicals are formed as a byproduct of trapping and are said to decay mainly by combination and disproportionation. 

Fig. 26. Ion images of phenyl radical obtained from the photodissociation of ethylbenzene at 248 nm at two different delay times (a) 15 ps, (b) 32 ps. (c) Intensity decay of the disk-like image as a function of delay times. A decay rate of 10B s 1 was obtained, (d) The fragment translational energy distribution for the reaction C6HbC2Hb -> C6HbCH2 + CH3.

Such decay is known as concerted fragmentation. Peroxides have the weak O—O bond and usually decompose with dissociation of this bond. The rate constants of such decomposition of ROOR into RO radicals demonstrate a low sensitivity of the BDE of the O—O bond to the structure of the R fragment [4], Bartlett and Hiat [8] studied the decay of many peresters and found that the rate constants of their decomposition covered a range over 105 s-1. The following mechanism of decomposition was proposed in parallel with a simple dissociation of one O—O bond [3,4] ... 

Three different mechanisms of perester homolytic decay are known [3,4] splitting of the weakest O—O bond with the formation of alkoxyl and acyloxyl radicals, concerted fragmentation with simultaneous splitting of O—O and C—C(O) bonds [3,4], and some ortho-substituted benzoyl peresters are decomposed by the mechanism of decomposition with anchimeric assistance [3,4]. The rate constants of perester decomposition and values of e = k l2kd are collected in the Handbook of Radical Initiators [4]. The yield of cage reaction products increases with increasing viscosity of the solvent. 

AN+- (Reitstoen and Parker, 1991). In other words, the triad of reactive fragments produced in (63) in the charge-transfer excitation of the EDA complex with A-nitropyridinium ion is susceptible to mutual (pairwise) annihilations leading to the Wheland intermediate W and the nucleophilic adduct N (Scheme 12), so that the observed second-order rate constant ku for the spectral decay of ArH+- in Table 3 actually represents a composite of k2 and k2. A similar competition between the homolytic and nucleophilic reactivity of aromatic cation radicals is observed in the reaction triad (55)... 

This step will undoubtedly dominate, since the CC bond is substantially weaker than any of the CH bonds in the molecule. As mentioned in the previous section, the radicals R and R" (fragments of the original hydrocarbon molecule RH) decay into olefins and H atoms. At any reasonable combustion temperature, some CH bonds are broken and H atoms appear owing to the initiation step... 

Figures 4.6—4.8 are the results for the stoichiometric propane-air flame. Figure 4.6 reports the variance of the major species, temperature, and heat release Figure 4.7 reports the major stable propane fragment distribution due to the proceeding reactions and Figure 4.8 shows the radical and formaldehyde distributions—all as a function of a spatial distance through the flame wave. As stated, the total wave thickness is chosen from the point at which one of the reactant mole fractions begins to decay to the point at which the heat release rate begins to taper off sharply. Since the point of initial reactant decay corresponds closely to the initial perceptive rise in temperature, the initial thermoneutral period is quite short. The heat release rate curve would ordinarily drop to zero sharply except that the recombination of the radicals in the burned gas zone contribute some energy. The choice of the position that separates the preheat zone and the reaction zone has been made to account for the slight exothermicity of the fuel attack reactions by radicals which have diffused into...

Figure 20.5. A graphical representation of the time evolution of transients for the Norrish type-I a-cleavage 43 and 46 amu fragments from acetone and from acetone-de- The representative sets of data points ( for 43 amu, for 46 amu fragments) are modeled with simple buildup and decay response functions, I(t) = 4[exp(—t/t2) — exp(—f/x])] the time constants of buildup and decay are Ti and T2, respectively. A modest isotope effect on the characteristic time for formation of these acyl radicals (60 and 80 fs, respectively) and a more prominent —CH3/—CD3 effect on decays through loss of CO (420 and 670 fs, respectively) were recorded. ...

There are a number of non-electrochemical techniques that have proven invaluable in combination with electrochemical results in understanding the chemistry and the kinetics. Laser flash photolysis (LFP) is a well-established technique for the study of the transient spectroscopy and kinetics of reactive intermediates. The technique is valuable for the studying of the kinetics of the reactions of radical anions, particularly those that undergo rapid stepwise dissociative processes. The kinetics of fragmentation of radical anions can be determined using this method if (i) the radical anion of interest can be formed in a process initiated by a laser pulse, (ii) it has a characteristic absorption spectrum with a suitable extinction coefficient, and (iii) the rate of decay of the absorption of the radical anion falls within the kinetic window of the LFP technique typically this is in the order of 1 x 10" s to 1 X 10 s . 

One of the first kinetic studies of the fragmentation of a C—O bond in an ether radical anion was reported by Maslak and Guthrie. " In this study substituted benzyl phenyl ethers (as well as some other benzyl-type phenyl ethers) were treated with 2,4,6-tri-tert-butylnitrobenzene radical anion to produce ArCH20Ph or PhCH20Ar and the unimolecular decay of the anion radical was monitored using EPR. Despite some discrepancies between the values of the reported rate constants, ... 

With ketones which can eject radicals more stable than methyl, fragmentation competes more successfully with all physical processes than in acetone, and unsymmetrical ketones preferentially eject the more stable alkyl radical.309 Thus both methyl ethyl ketone310 and methyl isopropyl ketone311 yield chiefly acetyl and ethyl or isopropyl radicals. Half of the diethyl ketone molecules excited by 3130-A irradiation at 25° decompose from the excited singlet state before they can undergo intersystem crossing, and another 40% fragment from the triplet state.312 Both fluorescence and phosphorescence are extremely weak. The more rapid decomposition in both excited states relative to that observed in acetone almost eliminates competition from physical-decay processes. 

In the PES-studied gas-phase thermolysis of the azines 72 and 73 (96T1965) methacrylonitrile and propene were found in addition to molecular nitrogen, which is in accord with a [5 - 2 + 2+ 1] fragmentation of the five-membered rings. The primary process is the cleavage of the N-N single bond, which is followed by the decay of the iminyl radicals thus formed. 

A number of papers report investigations of the pyrolytic cleavage of aromatic hydrocarbons. The oxidation and pyrolysis of anisole at 1000 K have revealed first-order decay in oxygen exclusively via homolysis of the O—CH3 bond to afford phenol, cresols, methylcyclopentadiene, and CO as the major products.256 A study of PAH radical anion salts revealed that CH4 and H2 are evolved from carbene formation and anionic polymerization of the radical species, respectively.257 Pyrolysis of allylpropar-gyltosylamine was studied at temperatures of 460-500 °C and pressures of 10-16 Torr. The product mixture was dominated by hydrocarbon fragments but also contained SO2 from a proposed thermolysis of an intermediate aldimine by radical processes.258... 

Isomeric C Hn radical ions fragment not very differently by the different mass spectro-metric methods. The metastable decays are nearly identical, but the collisionally activated spectra of 14 isomeric hexenes, measured by Nishishita and McLafferty240, exhibit some quantitative differences. Bensimon, Rapin and Gaumann251 compared the metastable decay and the photoinduced fragmentation by infrared photons of long-lived parent ions of six hexene isomers and cyclohexane. If the linear isomers are practically identical, some notable differences are observed for branched isomers. Cyclohexane behaves similar to n-hexenes. The metastable fragmentation of H/D-labeled 4-Me-2-pentene, 2-Me-2-pentene... 

Similarly, the p-fragmentation of tertiary alkoxyl radicals [reaction (2)] is a well-known process. Interestingly, this unimolecular decay is speeded up in a polar environment. For example, the decay of the ferf-butoxyl radical into acetone and a methyl radical proceeds in the gas phase at a rate of 103 s 1 (for kinetic details and quantum-mechanical calculations see Fittschen et al. 2000), increases with increasing solvent polarity (Walling and Wagner 1964), and in water it is faster than 106 s 1 (Gilbert et al. 1981 Table 7.2). 

The rate of this reaction (which is the main decay of tertiary alkoxyl radicals) is also strongly enhanced in water as compared to the gas phase and organic solvents. If different substituents can be cleaved off, it is the more highly-substituted one (weaker C-C bond) that is broken preferentially (Riichardt 1987). Thus in the case of secondary alkoxyl radicals, substitution in p-position also decides the ratio of 1,2-H-shift and -fragmentation (Schuchmann and von Sonntag 1982). Because of the fast 1,2-H-shift and p-fragmentation reactions in water, intermolecular H-abstraction reactions of alkoxyl radicals [reaction (61)] are usually inefficient, but intramolecular H-abstraction may occur quite readily if an H atom is in a favorable distance (e.g., six-membered transition state). 

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