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Manganese Nitride Complexes in Oxidation States III, IV, and V: Synthesis and Electronic Structure

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    Manganese Nitride Complexes in Oxidation States III, IV, and V: Synthesis and Electronic Structure
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    † Department of Chemistry and Pharmacy, Inorganic Chemistry, Friedrich-Alexander University of Erlangen-Nuremberg, Egerlandstrasse 1, Erlangen, Germany
    ‡ Department of Chemistry and Chemical Biology, Cornell University, Ithaca, New York 14853, United States
    § Max-Planck-Institute for Chemical Energy Conversion (CEC), Stiftstrasse 34-36, D-45470 Mülheim an der Ruhr, Germany
    [email protected]
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    Journal of the American Chemical Society

    Cite this: J. Am. Chem. Soc. 2012, 134, 37, 15538–15544
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    https://doi.org/10.1021/ja306647c
    Published August 25, 2012
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    Abstract

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    The synthesis and characterization of a series of manganese nitrides in a tripodal chelating tris(carbene) ligand framework is described. Photolysis of [(TIMENxyl)Mn(N3)]+ (where TIMENxyl = tris[2-(3-xylylimidazol-2-ylidene)ethyl]amine) yields the isolable molecular MnIV nitride, [(TIMENxyl)Mn(N)]+. Spectroscopic and DFT studies indicate that this MnIV d3 complex has a doublet electronic ground state. The metal-centered one-electron oxidation of this MnIV species results in formation of the pentavalent MnV nitride, [(TIMENxyl)Mn(N)]2+. Unlike previously reported, tetragonal MnV nitrides with a d2, nonmagnetic S = 0 ground state, this trigonal bipyramidal complex has a triplet ground state S = 1. One-electron reduction of [(TIMENxyl)Mn(N)]+ produces the neutral, nonmagnetic trivalent [(TIMENxyl)Mn(N)] species with a d4 low-spin, S = 0, ground state.

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    Journal of the American Chemical Society

    Cite this: J. Am. Chem. Soc. 2012, 134, 37, 15538–15544
    Click to copy citationCitation copied!
    https://doi.org/10.1021/ja306647c
    Published August 25, 2012
    Copyright © 2012 American Chemical Society
    Request reuse permissions

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