Kinetics and Stoichiometry of Nitrogen Fixation with TiCl3-Mg and VCL3-Mg in Tetrahydrofuran

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Abstract
The kinetics and stoichiometry of nitrogen fixation with TiCl3-Mg and VCl3-Mg in tetrahydrofuran (THF) systems were studied. The systems react with molecular nitrogen at room temperature and normal pressure giving magnesium dichloride and nitrogen-containing complexes of compositions [MNMg2Cl2(THF)], where M=Ti and V, according to the stoichiometry: MCl3(THF)3+\frac52Mg+\frac12N2→[MNMg2Cl2(THF)]+\frac12MgCl2(THF)2. Properties of the isolated nitrogen-containing complexes were examined. Reactions under argon and hydrogen gave hydride-containing complexes. The initial rate of nitrogen fixation was first order with respect to the amounts of MCL3, Mg, and nitrogen pressure. A mechanism involving the complexation of N2 with dimeric M(II) species followed by rate-determining process to react with magnesium is proposed and discussed.