A Parent Iron Amido Complex in Catalysis of Ammonia Oxidation
Yongxian Li1, Jia-Yi Chen2, Qiyi Miao3,4
1School of Chemistry and Chemical Engineering, Shandong University, Jinan 250100, China.
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.
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