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 acri PNP‐pincer ligands {[( acri PNP)Ti] 2 ( μ 2 ‐ η 1 : η 2 ‐N 2 )( μ 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 ZnMe 2 , MgMe 2 , AlMe 3 , B(C 6 F 5 ) 3 , PinBH, and PhSiH 3 have been well established at the rigid acri 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.