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Characterization of Iron-Imido Species Relevant for N-Group Transfer Chemistry

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    Characterization of Iron-Imido Species Relevant for N-Group Transfer Chemistry
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    Department of Chemistry and Chemical Biology, Harvard University, 12 Oxford Street, Cambridge, Massachusetts 02138, United States
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    Cite this: J. Am. Chem. Soc. 2016, 138, 6, 1983–1993
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    https://doi.org/10.1021/jacs.5b12582
    Published January 20, 2016
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    Abstract

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    A sterically accessible tert-butyl-substituted dipyrrinato di-iron(II) complex [(tBuL)FeCl]2 possessing two bridging chloride atoms was synthesized from the previously reported solvento adduct. Upon treatment with aryl azides, the formation of high-spin FeIII species was confirmed by 57Fe Mössbauer spectroscopy. Crystallographic characterization revealed two possible oxidation products: (1) a terminal iron iminyl from aryl azides bearing ortho isopropyl substituents, (tBuL)FeCl(•NC6H3-2,6-iPr2); or (2) a bridging di-iron imido arising from reaction with 3,5-bis(trifluoromethyl)aryl azide, [(tBuL)FeCl]2(μ-NC6H3-3,5-(CF3)2). Similar to the previously reported (ArL)FeCl(•NC6H4-4-tBu), the monomeric iron imido is best described as a high-spin FeIII antiferromagnetically coupled to an iminyl radical, affording an S = 2 spin state as confirmed by SQUID magnetometry. The di-iron imido possesses an S = 0 ground state, arising from two high-spin FeIII centers weakly antiferromagnetically coupled through the bridging imido ligand. The terminal iron iminyl complex undergoes facile decomposition via intra- or intermolecular hydrogen-atom abstraction (HAA) from an imido aryl ortho isopropyl group, or from 1,4-cyclohexadiene, respectively. The bridging di-iron imido is a competent N-group transfer reagent to cyclic internal olefins as well as styrene. Although solid-state magnetometry indicates an antiferromagnetic interaction between the two iron centers (J = −108.7 cm–1) in [(tBuL)FeCl]2(μ-NC6H3-3,5-(CF3)2), we demonstrate that in solution the bridging imido can facilitate HAA as well as dissociate into a terminal iminyl species, which then can promote HAA. In situ monitoring reveals the di-iron bridging imido is a catalytically competent intermediate, one of several iron complexes observed in the amination of C–H bond substrates or styrene aziridination.

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    The Supporting Information is available free of charge on the ACS Publications website at DOI: 10.1021/jacs.5b12582.

    • General experimental considerations and procedures, multinuclear NMR data, 57Fe Mössbauer and EPR spectra, magnetometry data, solid-state molecular structures, computational details, and crystallographic CIF files and crystallography data (PDF)

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    Cite this: J. Am. Chem. Soc. 2016, 138, 6, 1983–1993
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