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Parent amido complexes are crucial intermediates in ammonia-based transformations. We report a well-defined ferric ammine system Cp*Fe(1,2-Ph 2 PC 6 H 4 NH)(NH 3 ) + ( 1 -NH 3 + ), which processes electrocatalytic ammonia oxidation to N 2 and H 2 at a mild potential. Through establishing elementary e – /H + conversions with the ferric ammine, a formal Fe(IV)-amido species, 1 -NH 2 +, together with its conjugated Lewis acid, 1 -NH 3 2 +, was isolated and structurally characterized for the first time. Mechanism studies indicated that further oxidation of 1 -NH 2 + induces the reaction of the parent amido unit with NH 3 . 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.
Li et al. (Wed,) studied this question.