A Parent Iron Amido Complex in Catalysis of Ammonia Oxidation
Yongxian Li, Jiayi Chen, Qiyi Miao, Xin Yu, Lei Feng, Rong‐Zhen Liao, Shengfa Ye, Chen‐Ho Tung, Wenguang Wang
Abstract
Parent amido complexes are crucial intermediates in ammonia-based transformations. We report a well-defined ferric ammine system [Cp*Fe(1,2-Ph2PC6H4NH)(NH3)]+ ([1-NH3]+), which processes electrocatalytic ammonia oxidation to N2 and H2 at a mild potential. Through establishing elementary e–/H+ conversions with the ferric ammine, a formal Fe(IV)-amido species, [1-NH2]+, together with its conjugated Lewis acid, [1-NH3]2+, was isolated and structurally characterized for the first time. Mechanism studies indicated that further oxidation of [1-NH2]+ induces the reaction of the parent amido unit with NH3. The formation of hydrazine is realized by the non-innocent nature of the phenylamido ligand that facilitates the concerted transfer of one proton and two electrons.