Density-Functional Study of (Solvated) Grignard Complexes

Abstract

Density Functional calculations have been used to study the solvent effect of diethyl ether on the Schlenk equilibrium and the aggregation of Grignard reagents RMgX with R = Me, Et, Ph. Solvent stabilization of the Mg complexes of the first solvent is larger than that of the second one. The solvation energy decreases on going from the dihalides MgX₂ to the monohalides RMgX to the diorganyl compounds MgR₂. The calculations indicate that the energetic preference of the unsymmetrical species reduces upon solvation. The strong tendency to dimerization of the un- and partly solvated compound vanishes for the higher solvated cases.