Selective Catalytic Reduction of N2 to N2H4 by a Simple Fe Complex

Peter J Hill; Laurence R Doyle; Andrew D Crawford; William K Myers; Andrew E Ashley

doi:10.1021/jacs.6b08802

Selective Catalytic Reduction of N₂ to N₂H₄ by a Simple Fe Complex

J Am Chem Soc. 2016 Oct 19;138(41):13521-13524. doi: 10.1021/jacs.6b08802. Epub 2016 Oct 11.

Authors

Peter J Hill¹, Laurence R Doyle¹, Andrew D Crawford¹, William K Myers², Andrew E Ashley¹

Affiliations

¹ Department of Chemistry, Imperial College London , Imperial College Road, South Kensington, London SW7 2AZ, United Kingdom.
² Centre for Advanced Electron Spin Resonance, Inorganic Chemistry Laboratory, University of Oxford , South Parks Road, Oxford OX1 3QR, United Kingdom.

PMID: 27700079
DOI: 10.1021/jacs.6b08802

Abstract

The catalytic fixation of N₂ by molecular Fe compounds is a rapidly developing field, yet thus far few complexes can effect this transformation, and none are selective for N₂H₄ production. Herein we report that the simple Fe(0) complex Fe(Et₂PCH₂CH₂PEt₂)₂(N₂) (1) is an efficient catalyst for the selective conversion of N₂ (>25 molecules N₂ fixed) into N₂H₄, attendant with the production of ca. one molecule of NH₃. Notably, the reductant (CoCp*₂) and acid (Ph₂NH₂OTf) used are considerably weaker than conventional chemical H⁺ and e^- sources used in previous demonstrations of N₂ turnover by synthetic Fe compounds. These results show that the direct catalytic conversion of N₂ to the hydrazine oxidation state on molecular Fe complexes is viable and that the mechanism of NH₃ formation by such systems may proceed via Fe-N₂H₄ intermediates.

Publication types

Research Support, Non-U.S. Gov't