Activation Of Ammonia And Hydrazine By Electron Rich Fe(ii ...

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Chemical Science

Activation of ammonia and hydrazine by electron rich Fe(ii) complexes supported by a dianionic pentadentate ligand platform through a common terminal Fe(iii) amido intermediate†‡

Lucie Nurdin,a Yan Yang,b Peter G. N. Neate,c Warren E. Piers, *a Laurent Maron, *b Michael L. Neidig,*c Jian-Bin Lina and Benjamin S. Gelfand a Author affiliations

* Corresponding authors

a Department of Chemistry, University of Calgary, 2500 University Drive NW, Calgary, Alberta, Canada E-mail: [email protected]

b LPCNO, Université de Toulouse, INSA, UPS, Toulouse, France

c Department of Chemistry, University of Rochester, Rochester, New York 14627, USA

Abstract

We report the use of electron rich iron complexes supported by a dianionic diborate pentadentate ligand system, B2Pz4Py, for the coordination and activation of ammonia (NH3) and hydrazine (NH2NH2). For ammonia, coordination to neutral (B2Pz4Py)Fe(II) or cationic [(B2Pz4Py)Fe(III)]+ platforms leads to well characterized ammine complexes from which hydrogen atoms or protons can be removed to generate, fleetingly, a proposed (B2Pz4Py)Fe(III)–NH2 complex (3Ar-NH2). DFT computations suggest a high degree of spin density on the amido ligand, giving it significant aminyl radical character. It rapidly traps the H atom abstracting agent 2,4,6-tri-tert-butylphenoxy radical (ArO˙) to form a C–N bond in a fully characterized product (2Ar), or scavenges hydrogen atoms to return to the ammonia complex (B2Pz4Py)Fe(II)–NH3 (1Ar-NH3). Interestingly, when (B2Pz4Py)Fe(II) is reacted with NH2NH2, a hydrazine bridged dimer, (B2Pz4Py)Fe(II)–NH2NH2–Fe(II)(B2Pz4Py) ((1Ar)2-NH2NH2), is observed at −78 °C and converts to a fully characterized bridging diazene complex, 4Ar, along with ammonia adduct 1Ar-NH3 as it is allowed to warm to room temperature. Experimental and computational evidence is presented to suggest that (B2Pz4Py)Fe(II) induces reductive cleavage of the N–N bond in hydrazine to produce the Fe(III)–NH2 complex 3Ar-NH2, which abstracts H˙ atoms from (1Ar)2-NH2NH2 to generate the observed products. All of these transformations are relevant to proposed steps in the ammonia oxidation reaction, an important process for the use of nitrogen-based fuels enabled by abundant first row transition metals.

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Supplementary files

• Supplementary information PDF (5508K)
• Crystal structure data CIF (1186K)

Article information

DOI https://doi.org/10.1039/D0SC06466A Article type Edge Article Submitted 24 Nov 2020 Accepted 21 Dec 2020 First published 22 Dec 2020 This article is Open Access All publication charges for this article have been paid for by the Royal Society of Chemistry

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Chem. Sci., 2021,12, 2231-2241 BibTex EndNote MEDLINE ProCite ReferenceManager RefWorks RIS

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Activation of ammonia and hydrazine by electron rich Fe(II) complexes supported by a dianionic pentadentate ligand platform through a common terminal Fe(III) amido intermediate

L. Nurdin, Y. Yang, P. G. N. Neate, W. E. Piers, L. Maron, M. L. Neidig, J. Lin and B. S. Gelfand, Chem. Sci., 2021, 12, 2231 DOI: 10.1039/D0SC06466A

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Lucie Nurdin Yan Yang Peter G. N. Neate Warren E. Piers Laurent Maron Michael L. Neidig Jian-Bin Lin Benjamin S. Gelfand

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