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Ermert DM, Gordon JB, Abboud KA, et al. Nitride-bridged triiron complex and its relevance to dinitrogen activation. Inorg Chem. 2015;54(19):9282-9doi: 10.1021/acs.inorgchem.5b00825.
Ermert, D. M., Gordon, J. B., Abboud, K. A., & Murray, L. J. (2015). Nitride-bridged triiron complex and its relevance to dinitrogen activation. Inorganic chemistry, 54(19), 9282-9. https://doi.org/10.1021/acs.inorgchem.5b00825
Ermert, David M, et al. "Nitride-bridged triiron complex and its relevance to dinitrogen activation." Inorganic chemistry vol. 54,19 (2015): 9282-9. doi: https://doi.org/10.1021/acs.inorgchem.5b00825
Ermert DM, Gordon JB, Abboud KA, Murray LJ. Nitride-bridged triiron complex and its relevance to dinitrogen activation. Inorg Chem. 2015 Oct 05;54(19):9282-9. doi: 10.1021/acs.inorgchem.5b00825. Epub 2015 Jun 08. PMID: 26052673.
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Inorg Chem. 2015 Oct 05;54(19):9282-9. doi: 10.1021/acs.inorgchem.5b00825. Epub 2015 Jun 08.

Nitride-bridged triiron complex and its relevance to dinitrogen activation.

Inorganic chemistry

David M Ermert, Jesse B Gordon, Khalil A Abboud, Leslie J Murray

Affiliations

  1. Department of Chemistry, Center for Catalysis, University of Florida , Gainesville, Florida 32611, United States.

PMID: 26052673 DOI: 10.1021/acs.inorgchem.5b00825

Abstract

Using a simple metathesis approach, the triiron(II) tribromide complex Fe3Br3L (1) reacts with tetrabutylammonium azide to afford the monoazide dibromide analogue Fe3(Br)2(N3)L (2) in high yield. The inclusion of azide was confirmed by IR spectroscopy with a ν(N3) = 2082 cm(-1) as well as combustion analysis and X-ray crystallography. Heating 2 in the solid state results in the complete loss of the azide vibration in the IR spectra and the isolation of the olive-green mononitride complex Fe3(Br)2(N)L (3). Solution magnetic susceptibility measurements support that the trimetallic core within 2 is oxidized upon generation of 3 (5.07 vs 3.09 μB). Absorption maxima in the UV-visible-near-IR (NIR) spectra of 2 and 3 support the azide-to-nitride conversion, and a broad NIR absorption centered at 1117 nm is similar to that previously reported for the intervalence charge-transfer band for a mixed-valent nitridodiiron cluster. The cyclic voltammograms recorded for 3 are comparable to those of 1 with no reductive waves observed between ∼0 and -2.5 V (vs Fc/Fc(+)), whereas a reversible one-electron redox process is observed for Fe3(NH2)3L (4). These results suggest that intercluster cooperativity is unlikely to predominate the dinitrogen reduction mechanism when 1 is treated with KC8 under N2.

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