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

Studies on N-2 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)-P-acri-pincer ligands {[((PNP)-P-acri)Ti](2)(mu(2)-eta(1):eta(2)-N-2)(mu(2)-H)(2)} are presented. This complex enabled N-2 cleavage and hydrogenation even without additional H-2 or other reducing agents. Furthermore, diverse transformations of the N-2 unit with a variety of organometallic compounds such as ZnMe2, MgMe2, AlMe3, B(C6F5)(3), PinBH, and PhSiH3 have been well established at the rigid (PNP)-P-acri-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.