含金属氮多重键的过渡金属亚胺化合物由于在含氮基团转移反应以及催化等领域的应用而成为配位化学和有机金属化学的重要研究内容之一。而随着金属中心d电子数的增加，第八族（“氧墙”）以后的后过渡金属亚胺化合物的合成变得较为困难。本项目拟设计合成基于双齿含氮配体的低价态铱铑（一价）的有机金属化合物，并以此为前驱体利用叠氮化物氧化分解的方法制备第九族铱铑（三价）亚胺化物；并进一步探索它们与烯烃小分子间的反应性以及在碳氮键构筑如烯烃氢胺化反应中的催化应用。本项目的实施将有助于揭示取代基的电子和位阻效应对铱铑亚胺化合物稳定性和反应性的影响，阐明后过渡金属亚胺化合物对烯烃的活化机制；在此基础上实现对金属亚胺化合物催化活性的调控，为含金属亚胺基元的催化剂的设计开发提供理论和实验依据。

Transition metal imido complex containing metal-nitrogen multiple bond is an important class in coordination chemistry and organometallic chemistry because of their application in NR group transfer reaction and catalysis. As the increase of d electrons of the metal center, the synthesis of late transition metal imido complexes which on the right of group 8 transition metal (“oxo wall”) became very difficult. In this project, we attempt to design and prepare the low oxidation iridium and rhodium organometallic compounds based on bidentate ligands with N donor, then the group 9 iridium and rhodium imido complexes were synthesized through the oxidative reaction between the low oxidation organometallic compounds with azides. The reactivity of these imido complexes with small molecules as well as their application in carbon-nitrogen bond formation reaction (such as hydroamination reaction) will be also explored. The accomplishment of this project is expected to uncover the relationship of the electronic and steric effects of the substituents to the stability and reactivity of the iridium and rhodium imido complexes, and elaborate the activation mechanism between late transition metal imido complexes and alkenes; thus the catalytic activity of the imido complexes can be tuned based on these results. This provides theoretical and experimental basis for the development of the catalyst containing metal imido motif.