Densities, carbon radical

Carbon Radical Densities. The radical densities are the most variable of the quantities encountered, and perhaps the most... 

In the step above, Br attacked the alkene at the less substituted carbon, in order to form the more substituted carbon radical (C ). Tertiary radicals are more stable than secondary radicals, for the same reason that tertiary carbocations are more stable than secondary carbocations. Just as alkyl groups donate electron density to... 

A type iii-d reaction leads to the formation of (69). Trifluoromethyl radicals generated electrochemically from triflu-oroacetate can attack electron-deficient olefins leading to trifluoromethylated carbon radicals whose chemical and electrochemical follow-up reactions can be controlled by current density, reaction temperature, and substituents of the olefins. With fumaronitrile (86) at 50 °C the monotri-fluoromethylated compound (87) was obtained in 65% yield (Scheme 31) [110]. 

Products from the electrochemical oxidation of cyclohexene (Scheme 2.1) illustrate the general course of reaction [28, 29]. The radical-cation either undergoes loss of an allylic proton or reacts, at the centre of liighest positive charge density, with a nucleophile. Either reaction leads to a carbon radical, which is oxidised to the carbonium ion. A Wagncr-Meerwein rearrangement then gives the most stable carbonium ion, which subsequently reacts with a nucleophile. 

Any molecular entity possessing an unpaired electron. The modifier unpaired is preferred over free in this context. The term free radical is to be restricted to those radicals which do not form parts of radical pairs. Further distinctions are often made, either by the nature of the central atom having the unpaired electron (or atom of highest electron spin density) such as a carbon radical (e.g., -CHs) or whether the unpaired electron is in an orbital having more s character (thus, radical molecular entity in a manuscript, the structure should always be written with a superscript dot or, preferably, a center-spaced bullet (e.g., -OH, -CHs, CF). 

Free Radicals in Macerals. Electron spin resonance (ESR) has been used to study carbon free radicals in coals, and to some extent, separated macerals. The technique provides information on radical density and the environment of the radicals. The resonance position, termed the g-value, is dependent on the structure of the molecule which contains the free electron. The line width is also sensitive to the environment of the unpaired electron. In an early study, Kroger (71) reported that the spin concentration varied between maceral groups with liptinite < vitrinite inertinite. For this limited set of samples the spin concentration increases with rank for liptinites and vitrinites and decreases for the micrinite samples. On the other hand, van Krevelen (72) found the same general results except... 

Electron spin resonance determinations of g-values, linewidths, radical densities and saturation properties have been performed on carbon radicals in samples of coal macerals isolated by density gradient centrifugation techniques. These data are compared with elemental analyses and density measurements. Each maceral type exhibits a different ESR signature" which can be understood in terms of the nature of the starting organic and the extent of coalification. 

There have been a large number of electron spin resonance (ESR) studies of coal and coal products,(1J but a microscopic interpretation of the resulting data has been hampered by the chemical heterogeneity of the coal samples examined. While several surveys of specially selected macerals have appeared, 3), the recent evolution of maceral separation techniques - now allows detailed ESR observations to be made on coals systematically fractionated in which coal rank, maceral type, and maceral density are simultaneously distinguished. The present report surveys the behavior of a variety of ESR properties of carbon radicals in exinite, vitrinite, and inertinite macerals in a variety of coals of different rank. These data... 

These ESR observations focus on carbon radicals, unpaired electrons in the carbonaceous matrix of the macerals associated with incomplete carbon bonds. In the macerals surveyed here, these radical densities span a substantial range of values from 4 x 1018 radical spins/g-carbon for some subbituminous... 

Tetramethyl-4-heptene-3-one (125 in Eq. (193)) was reduced in dipolar aprotic media (DMF, HMTPA) to its radical anion 126 418 The ESR spectrum indicated 40—50% of the radical density at the 3-carbon, and the rest at the carbonyl carbon and oxygen, but nothing at the cx. -carbon. 126 dimerizes to the tail-to-tail dimer at a rate which is the faster the more effectively the electrostatic repulsion of the two radical anions is reduced. With Li+ as counterion the half life of 126 is less than 10 1 sec, with Na+ or Pr4N+ 10 to 50 sec. 

A second result of Importance in the ESR studies was the measurement of a signal In the deactivated samples that could be assigned to carbon free radicals. This correlated very well with weight % carbon on catalyst for the composite samples as shown in Figure 6. There was no correlation between either carbon free radical density or coke on catalyst and hydrogenation activity,... 

The rebound mechanism, though in a modified version, has been recently supported by theoretical calculations of KIF using the density functional theory (Yoshizawa et al., 2000). The calculations demonstrate that the transition state for the H-atom abstraction from ethane involves a linear [FeO.H...C] array a resultant radical species with a spin density of nearly one is bound to an iron-hydroxy complex, followed by recombination and release of product ethanol. According to the calculation of the reaction energy profile, the carbon radical species is not a stable reaction intermediate with a finite lifetime. The calculated KIF at 300 K is in the range of 7-13 in accord with experimental data and is predicted to be significantly dependent on temperature and substituents. It was also shown from femtosecond dynamic calculations in the FeOVCH4 system that the direct abstraction mechanism can occur in 100-200 fs. 

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