Synthesis and Diverse Transformations of a Dinitrogen Dititanium Hydride Complex Bearing Rigid Acridane-Based PNP-Pincer Ligands.

Studies on N activation and transformation by transition metal hydride complexes are of particular interest and importance. The synthesis and diverse transformations of a dinitrogen dititanium hydride complex bearing the rigid acridane-based PNP-pincer ligands {[( PNP)Ti] (μ -η :η -N )(μ -H) } are presented. This complex enabled N cleavage and hydrogenation even without additional H or other reducing agents. Furthermore, diverse transformations of the N unit with a variety of organometallic compounds such as ZnMe , MgMe , AlMe , B(C F ) , PinBH, and PhSiH have been well established at the rigid PNP-ligated dititanium framework, such as reversible bonding-mode change between the end-on and side-on/end-on fashions, diborylative N=N bond cleavage, the formal insertion of two dimethylaluminum species into the N=N bond, and the formal insertion of two silylene units into the N=N bond. This work has revealed many unprecedented aspects of dinitrogen reaction chemistry.