Mo Zhenbo, Shima Takanori, Hou Zhaomin
Organometallic Chemistry Laboratory, RIKEN Cluster for Pioneering Research, 2-1 Hirosawa, Wako, Saitama, 351-0198, Japan.
Advanced Catalysis Research Group, RIKEN Center for Sustainable Resource Science, 2-1 Hirosawa, Wako, Saitama, 351-0198, Japan.
Angew Chem Int Ed Engl. 2020 May 25;59(22):8635-8644. doi: 10.1002/anie.201916171. Epub 2020 Mar 18.
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.
关于过渡金属氢化物配合物对氮的活化和转化的研究具有特别的意义和重要性。本文报道了一种带有刚性吖啶基PNP钳形配体{[(PNP)Ti](μ -η:η -N)(μ -H)}的二氮二钛氢化物配合物的合成及其多样的转化反应。即使没有额外的氢气或其他还原剂，该配合物也能实现氮的裂解和氢化反应。此外，在刚性的PNP配位二钛骨架上，已充分证实了氮单元与多种有机金属化合物（如ZnMe₂、MgMe₂、AlMe₃、B(C₆F₅)₃、PinBH和PhSiH₃）之间的多样转化反应，如端基配位和侧基/端基配位方式之间的可逆键合模式变化、双硼化氮氮键裂解、两个二甲基铝物种对氮氮键的形式插入以及两个硅烯单元对氮氮键的形式插入。这项工作揭示了许多前所未有的二氮反应化学方面的内容。
