It has been recently shown that alkylated titanocene complexes of the type Cp*Ti(CH2SiMe3)3 (Cp* = η5-C5Me5) bearing cyclopentadienyl ligands are capable of splitting dinitrogen under mild conditions. In our laboratory, we have been investigating the coordination chemistry of imidazolin-2-iminato ligands (ImN), which can be considered as Cp-ligand electronic analogs. Motivated by the recent nitrogen fixation chemistry of titanocene alkyl compounds, we have begun investigating the reactivity of ImN-[Ti] complexes. We envision that the enhanced electron donation of the ImN- ligand will afford electron-rich titanium compounds capable of activating N2 upon reduction. In support of this idea, preliminary results show that the reduction of (ImN)TiCl3 cleaves the triple bond in N2 to produce a novel [Ti6N6] dicubane cluster. The synthesis of a handful of Ti(IV) and Ti(III) compounds of the form (ImN)TiX3, (ImN)2TiX2 (X = Cl; alkyl) and their reduction chemistry will be discussed.

Reduction of titanium imidazolin-2-iminato complexes for the activation and cleavage of N2

255th National Meeting (2018)

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