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Updated: Oct 21, 2025

The Synthesis, Characterization and Reactivity of a Series of Ruthenium N-triphosPh Complexes
Published on: April 10, 2015
Synthesis, Structure, and Ammonia Oxidation Catalytic Activity of Ru-NH3 Complexes Containing Multidentate
Jan Holub1, Nataliia Vereshchuk1,2, Francisco-Javier Sánchez-Baygual1
1Institute of Chemical Research of Catalonia, Barcelona Institute of Science and Technology, Avda. Països Catalans 16, 43007 Tarragona, Spain.
Abstract:
Ammonia (electro)oxidation with molecular catalysts is a rapidly developing topic with wide practical applications ahead. We report here the catalytic ammonia oxidation reaction (AOR) activity using [Ru(tda-κ-N3O)(py)2], 2, (tda2- is 2,2':6',2''-terpyridine-6,6''-dicarboxylate; py is pyridine) as a catalyst precursor. Furthermore, we also describe the rich chemistry associated with the reaction of Ru-tda and Ru-tPa (tPa-4 is 2,2':6',2''-terpyridine-6,6''-diphosphonate) complexes with NH3 and N2H4 using [RuII(tda-κ-N3O)(dmso)Cl] (dmso is dimethyl sulfoxide) and [RuII(tPa-κ-N3O)(py)2], 8, as synthetic intermediates, respectively. All the new complexes obtained here were characterized spectroscopically by means of UV-vis and NMR. In addition, a crystal X-ray diffraction analysis was performed for complexes trans-[RuII(tda-κ-N3)(py)2(NH3)], 4, trans-[RuII(tda-κ-N3)(N-NH2)(py)2], 5, cis-[RuII(tda-κ-N3)(py)(NH3)2], 6 (30%), and cis-[RuII(tda-k-N3)(dmso)(NH3)2], 7 (70%). The AOR activity associated with 2 and 8 as catalyst precursors was studied in organic and aqueous media. For 2, turnover numbers of 7.5 were achieved under bulk electrolysis conditions at an Eapp = 1.4 V versus normal hydrogen electrode in acetonitrile. A catalytic cycle is proposed based on electrochemical and kinetic evidence.
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