Solvent Effects in the Reactions of Free Radicals and Atoms. II. Effects of Solvents on the Position of Attack of Chlorine Atoms upon 2,3-Dimethylbutane, Isobutane and 2-Deuterio-2-methylpropane¹

Selectivity in Thermal 34mCl-for-CI Exchange with Chlorobenzenes

“…The selectivity for the photochlorination of 2,3-DBM in benzene, as observed by RUSSELL [13], increases with decreasing DMB concentrations [41]. This was explained by reactions of the chlorocyclohexadienyl radical (acomplex):…”

“…RUSSELL [13] concluded from photochlorination experiments of 2,3-dimethylbutane (DMB), dissolved in substituted benzenes, that the primary reaction, abstraction of an H atom from DMB does not proceed by free Cl atoms, but by Q atoms bound in aromatic w-complexes which have a lower reactivity and hence a greater selectivity than free Cl atoms. The stability of such 7r-complexes increases with the basicity or electron density in the aromatic ring, which is linked to the electron-supplying properties of the substituent.…”

Reactions of Recoil F- and Cl-Atoms with Liquid Aromatic Compounds and Additives

“…Thermal C1 atoms can be loosely bound in an aromatic TT-complex, which results in a lower reactivity and a greater selectivity for the abstraction of H atoms from aliphatic Compounds by these C1 atoms [5][6][7]. Furthermore it has been found that Brj and I^ decrease the '"'"''«Cl-for-Cl replacement yield in C^HsCl to a large extent, in particular for ^®Cl-recoil atoms [3,8,9].…”

“…RUSSELL [7] has proven that C1 atoms bound in a 7r-aromatic complex retain most of their reactivity.…”

Photochemistry of CS2/Cl complexes—combined pulse radiolysis–laser flash photolysis studies

“…Chlorine atom complexes with arenes or carbon disulfide (CS 2 ) have been shown to be transient species which have high tertiary/primary selectivity in chlorination reactions of 2,3-dimethylbutane (Russell, 1958a(Russell, , 1958b. The spectroscopic and kinetic studies of these complexes have been conducted extensively (Ingold et al, 1990;Chateauneuf, 1993).…”