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Updated: May 9, 2025

The Synthesis, Characterization and Reactivity of a Series of Ruthenium N-triphosPh Complexes
Published on: April 10, 2015
Electrocatalytic Ammonia Oxidation by a Ruthenium Complex Bearing a 2,6-Pyridinedicarboxylate Ligand
Jun Li1,2,3, Xiaohuo Shi4, Feiyang Zhang1,2,3
1Department of Chemistry, Zhejiang University, Hangzhou, Zhejiang 310058, China.
Abstract:
Molecular catalysts for the electrocatalytic ammonia oxidation reaction (eAOR) have much to offer in terms of mechanistic investigations and practical energy issues. This work reports the use of complex [Ru(pdc-κ-N1O2)(bpy)(NH3)] (Ru-NH 3 ) (H2pdc = 2, 6-pyridinedicarboxylic acid; bpy = 2,2'-bipyridine) bearing a readily accessible pdc2- ligand to catalyze ammonia oxidation under electrochemical conditions. The rich structural variations of Ru-NH 3 in coordinating solvents and an ammonia atmosphere were fully characterized by cyclic voltammograms (CVs), NMR, and XRD. CV experiments showed that Ru-NH 3 promotes electrocatalytic ammonia oxidation at a low overpotential of 0.85 V with a calculated catalytic rate (k obs) of 18.9 s-1. Controlled potential electrolysis (CPE) at an applied potential of 0.3 V vs Fc+/0 achieves 76.1 equiv of N2 with a faradaic efficiency of 89.8%. Experimental and computational analyses indicated that oxidation of Ru-NH 3 generates a reactive Ru III -NH 3 intermediate, which undergoes sequential electron and proton transfer steps to form a Ru VI ≡N species. N-N bond formation occurs via the nucleophilic attack of an ammonia molecule on the Ru VI ≡N moiety with a facile barrier of 8.6 kcal/mol. Eventually, N2 evolved as the product after releasing two electrons and three protons.
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