title: Grignard reaction with chlorosilanes in THF: a kinetic study.
abstract: Kinetics of the reactions of phenylmagnesium chloride and bromide and diphenylmagnesium with chlorosilanes were investigated in tetrahydrofurane (THF) and in THF-hydrocarbon mixtures. The reaction in THF is much faster than that in diethyl ether. Assuming coordination of magnesium halides with three molecules of THF, concentrations of all the species involved in Schlenk equilibrium were calculated. In the Grignard reaction, species R(2)Mg and RMgX react competitively accompanied by additional reaction paths involving electrophilic catalysis by magnesium halide. This conclusion also proved to be valid for the Grignard reaction with a ketone and probably can be expanded to any Grignard reaction. When Schlenk equilibrium is shifted far to the RMgX species, the catalytic pathways are insignificant. Substituents at the silicon center control the rate of the reaction through their inductive and steric effects.
authors.affiliation: Institute of Organic and Bioorganic Chemistry, University of Tartu, Tartu 51014, Estonia. ants.tuulmets@ut.ee
authors.forename: Ants
authors.initials: A
authors.lastname: Tuulmets
authors.forename: Binh T
authors.initials: BT
authors.lastname: Nguyen
authors.forename: Dmitri
authors.initials: D
authors.lastname: Panov