Benzene radicals

Fig. 12.2. EPR spectra of small organic free radicals, (a) Spectrum of the benzene radical anion. [From J. R. Bolton, Mol. Phys. 6 219 (1963). Reproduced by permission of Taylor and Francis, Ltd.] (b) Spectrum of the ethyl radical. [From R. W. Fessenden and R. H. Schuler, J. Chem. Phys. 33 935 (1960) J. Chem. Phys. 39 2147 (1963). Reproduced by permission of the American Institute of Physics.]...

Theoretical and Experimental Studies of the Benzene Radical Cation Effects of Selective... 

In our previous study of the benzene radical cation [9], it was shown that computational methods which do not include correlation predict an erroneous... 

Table 1 Optimized Geometrical Parameters for the Benzene Radical Cation Ground State ( B3g), Obtained Using B3-LYP with Various Basis Sets.

Table 3 Vibrational Frequency Components in the High- and Low-Frequency regions (cm ) and Total ZPVE (kJ mol ) for the Non- and Mono-Deuterated Isomers of the Benzene Radical Cation.

The new branched polystyrene chain may eventually terminate, crosslinked by reacting with another polystyrene chain or an immobilised divinyl benzene radical. Grafting is thus enhanced mainly... 

Many other ion-molecule reactions involving highly unsaturated hydrocarbon ions and neutral olefins or the equivalent strained cycloalkanes have been studied by mass spectrometry98. For example, we may mention here the addition of ionized cyclopropane and cyclobutane to benzene radical cations giving the respective n-alkylbenzene ions but also isomeric cyclodiene ions such as ionized 8,9-dihydroindane and 9,10-dihydrotetralin, respectively. Extensive studies have been performed on the dimerization product of charged and neutral styrene4. 

A review considering the generation and characterization of radical ions, their reactions, formation of species with three-electron bonds, and radical cations of strained systems has been published." The redox and acidity properties of a number of substituted benzene radical cations were smdied by pulse radiolysis. ... 

The solute benzene radical cation was formed on pulse radiolysis of an acidic aqueous solution of benzene. The transient optical absorption bands (A-max = 310, 350-500 nm) were assigned to the solute benzene radical cation which is formed on acid-catalysed dehydration of the OH adduct. The radical cation is able to undergo an electron-transfer reaction with Br and was found to be a strong electron oxidant. Pulse radiolysis has been used to study the complex reaction that follows electron addition to hydroxybenzophenones (HOBPs). The various radical species involved have been characterized spectrally and their p/fa values evaluated. The differences... 

Table 6.2. Long wavelength uv absorption bands of benzene radical-cations in water, determined by pulse-radiolysis techniques.

Benzene radical-cation is formed at the anode and reacts with water as a nucleophile to form phenol as an intermediate. Phenol is more readily oxidised than benzene and is converted to 1,4-dihydroxybenzene. Further oxidation of this in the anode chamber leads to quinone. 

Arylsilane radical anions undergo cleavage and coupling reactions, usually under conditions where excess reducing agent is available. Reduction of phenylsilane, diphenylsilane, or triphenylsilane with sodium-potassium alloy under preparative conditions gives high yields of tetraphenylsilane (7). In the reduction of phenylsilanes, the appearance of 1,4-bis(silyl)benzene radical anions is frequently observed (135, 35, 86, 97, 75, 120, 100). Typical results are shown in Table II. 

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