Reactions of gases in solution. Part II. Kinetics of the reaction of nitrogen with titanium cyclopentadienyl complexes.

Abstract

The rate of the reaction of nitrogen with solutions of Ti(C₅H₅)₂Cl₂ and ethylmagnesium bromide in diethyl ether has been studied as a function of the concentration of the three reagents, temperature, and other variables. The rate increases approximately linearly with the concentration of the Grignard reagent up to a limiting value, which can be ascribed to reactions between the titanium complex and the Grignard reagent which precede the fixation step. The rate of fixation depends on the partial pressure of nitrogen at low p(N₂), but is virtually independent under 1 atmosphere of nitrogen, where the rate shows a second-order dependence on the titanium concentration and has an activation energy of approximately 4 kcal./mole.