Redox-Controlled and Reversible N-N Bond Forming and Splitting with an IronIVTerminal Imido Ligand

Aguilar-Calderón JR, Fehn D, Sorsche D, Miehlich M, Carroll PJ, Zars E, Meyer K, Mindiola DJ (2021)

Publication Type: Journal article

Publication year: 2021

Journal

Inorganic Chemistry American Chemical Society

DOI: 10.1021/acs.inorgchem.1c01509

Abstract

Oxidation of the low-spin FeIV imido complex [{(tBupyrr)2py}Feâ• NAd] (1) ((tBupyrr)2py2- = 2,6-bis(3,5-di-tert-butyl-pyrrolyl)pyridine, Ad = 1-adamantyl) with AgOAc or AgNO3 promotes reductive N-N bond coupling of the former imido nitrogen with a pyrrole nitrogen to form the respective ferric hydrazido-like pincer complexes [{(tBupyrrNAd)(tBupyrr)py}Fe(κ2-X)] (X = OAc-, 2OAc NO3-, 2NO3). Reduction of 2OAc with KC8 cleaves the N-N bond to reform the FeIV imido ligand in 1, whereas acid-mediated demetalation of 2OAc or 2NO3 yields the free hydrazine ligand [(tBupyrrNHAd)(tBupyrrH)py] (3), the latter of which can be used as a direct entry to the iron imido complex when treated with [Fe{N(SiMe3)2}2]. In addition to characterizing these Fe systems, we show how this nitrene transfer strategy can be expanded to Co for the one-step synthesis of Co{(tBu-NHAdpyrr)(tBupyrr)py}] (4) ((tBu-NHAdpyrr)(tBupyrr)py2- = 2-(3-tBu-5-(1-adamantylmethyl-2-methylpropane-2-yl)-pyrrol-2-yl)-6-(3,5-tBu2-pyrrol-2-yl)-pyridine).

Authors with CRIS profile

Dominik Fehn Lehrstuhl für Anorganische und Allgemeine Chemie Matthias Miehlich Lehrstuhl für Anorganische und Allgemeine Chemie Karsten Meyer Lehrstuhl für Anorganische und Allgemeine Chemie

Involved external institutions

University of Pennsylvania US United States (USA) (US)

How to cite

APA:

Aguilar-Calderón, J.R., Fehn, D., Sorsche, D., Miehlich, M., Carroll, P.J., Zars, E.,... Mindiola, D.J. (2021). Redox-Controlled and Reversible N-N Bond Forming and Splitting with an IronIVTerminal Imido Ligand. Inorganic Chemistry. https://doi.org/10.1021/acs.inorgchem.1c01509

MLA:

Aguilar-Calderón, J. Rolando, et al. "Redox-Controlled and Reversible N-N Bond Forming and Splitting with an IronIVTerminal Imido Ligand." Inorganic Chemistry (2021).

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