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Electrocatalytic Azide Oxidation Mediated by a Rh(PNP) Pincer Complex.
Christophe Rebreyend1, Yann Gloaguen1, Martin Lutz2
1Homogeneous and Supramolecular Catalysis van't Hoff Institute for Molecular Sciences (HIMS), University of Amsterdam, Amsterdam, The Netherlands.
Chemistry (Weinheim an Der Bergstrasse, Germany)
|September 13, 2017
Summary
Rhodium complexes can convert azide to dinitrogen. This catalytic oxidation of azide offers a potential pathway for cleaner fuel cells, producing only nitrogen gas.
Area of Science:
- Inorganic Chemistry
- Electrochemistry
- Catalysis
Background:
- Azido complexes of rhodium are of interest for nitrogen-based transformations.
- The development of efficient catalysts for nitrogen extrusion is crucial for energy applications.
Purpose of the Study:
- To investigate the one-electron oxidation of a rhodium(I) azido complex.
- To explore the catalytic potential of this complex in azide oxidation for energy applications.
Main Methods:
- Synthesis and characterization of the rhodium(I) azido complex [Rh(N3)(PNP)].
- Electrochemical oxidation studies of the complex in the presence of excess azide.
Main Results:
- One-electron oxidation of [Rh(N3)(PNP)] selectively forms the rhodium(I) dinitrogen complex [Rh(N2)(PNP)]+.
- The rhodium complex catalyzes electrochemical azide oxidation at approximately -0.23 V vs. Fc+/0.
Conclusions:
- The rhodium complex facilitates the conversion of azide to dinitrogen.
- This process has potential applications in the design of azide-based and direct ammonia fuel cells, with dinitrogen as the only byproduct.
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