V.V. Smirnov

Reactions of atomic magnesium in the basic state with organic chlorine derivatives at low temperatures

Abstract Low-temperature solid-phase reactions of atomic magnesium in the basic state with a number of aliphatic monochlorine derivatives, chlorobenzene, carbon tetrachloride and 1,2-dichloroethane, have been investigated. The nature of the intermediate particles is discussed, the effect of the phase state of a frozen hydrocarbon on its reactivity examined, and the mechanisms of reactions with the participation of radicals and ion radicals proposed.

Low-temperature reaction of magnesium with fluorobenzene

Abstract The low-temperature reaction of magnesium with fluorobenzene has been investigated. Joint condensation of magnesium and fluorobenzene vapours at low temperatures quantitatively gave phenylmagnesium fluoride in one stage.

Molecular mechanism of hydrogen bromide addition to olefins

Abstract Experimental results on the products and the kinetics of the hydrogen bromide addition to alkenes-1 in non-polar solvents and on complex formation in hydrogen bromide-olefin-solvent systems are reviewed. Theoretical calculations concerning hydrogen bromide-olefin complexes are used along with the experimental evidence to suggest a molecular mechanism of addition involving intermediate cyclic structures.

CNDO/2 calculations of intermolecular interactions in chlorine-ethylene and bromine-ethylene systems

Abstract SCF-MO-LCAO CNDO/2 calculations have been performed for 1:1 molecular complexes of ethylene with chlorine and bromine. The calculations predict for the chloro compound a structure with the Cl2 molecule normal to the ethylene plane and positioned above the centre of the double bond. A number of structures are energetically possible for the bromine compound including those with preferential interaction of Br2 with one of the CH2 groups. This implies that complexes of the composition 2Br2.C2H4 may exist.

The mechanism of 2-methylbutene-2 hydrohalogenation in solid phase

Abstract Complexes and reactions of 2-methylbutene-2 with hydrohalogen (HCl, HBr) have been studied in solid phase at 80–150 K. It has been found that 2-methylbutene-2 forms with HX complexes of 1:1 and 1:2 composition. Hydrohalogenation proceeds via the rearrangement of complex 2HX·C5H10 into complex of the addition product with HX. Kinetic equation depends on the reagents ratio. In excess of HX (1 kJ mole . The molecular mechanism of hydrohalogenation in solid phase has been proposed.