Ligand Tailoring Toward an Air-Stable Iron(V) Nitrido Complex

Keilwerth M, Grunwald L, Mao W, Heinemann FW, Sutter J, Bill E, Meyer K (2021)

Publication Type: Journal article

Publication year: 2021

Journal

DOI: 10.1021/jacs.0c11141

Abstract

A new supporting ligand, tris-[2-(3-mesityl-imidazol-2-ylidene)methyl]amine (TIMMNMes), was developed and utilized to isolate an air-stable iron(V) complex bearing a terminal nitrido ligand, which was synthesized by one-electron oxidation from the iron(IV) precursor. Single-crystal X-ray diffraction analyses of both complexes reveal that the metal-centered oxidation is escorted by iron nitride (FeN) bond elongation, which in turn is accompanied by the accommodation of the high-valence iron center closer to the equatorial plane of a trigonal bipyramid. This contrasts with the previous observation of the only other literature-known Fe(IV)N/Fe(V)N redox pair, namely, [PhB(tBuIm)3FeN]0/+. On the basis of 57Fe Mössbauer, EPR, and UV/vis electronic absorption spectroscopy as well as quantum chemical calculations, we identified the lesser degree of pyramidalization around the iron atom, the Jahn-Teller distortion, and the resulting nature of the SOMO to be the decisive factors at play.

Authors with CRIS profile

Involved external institutions

Max-Planck-Institut für Chemische Energiekonversion (MPI CEC) / Max-Planck-Institute for Chemical Energy Conversion Germany (DE)

How to cite

APA:

Keilwerth, M., Grunwald, L., Mao, W., Heinemann, F.W., Sutter, J., Bill, E., & Meyer, K. (2021). Ligand Tailoring Toward an Air-Stable Iron(V) Nitrido Complex. Journal of the American Chemical Society. https://dx.doi.org/10.1021/jacs.0c11141

MLA:

Keilwerth, Martin, et al. "Ligand Tailoring Toward an Air-Stable Iron(V) Nitrido Complex." Journal of the American Chemical Society (2021).

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