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    Spectroscopic and Computational Investigation of Low-Spin MnIII Bis(scorpionate) Complexes

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    Issue Date
    2016-06
    Author
    Colmer, Hannah Elizabeth
    Margarit, Charles G.
    Smith, Jeremy M.
    Jackson, Timothy A.
    Telser, Joshua
    Publisher
    Wiley
    Type
    Article
    Article Version
    Scholarly/refereed, author accepted manuscript
    Rights
    This is the peer reviewed version of the following article: Colmer, H. E., Margarit, C. G., Smith, J. M., Jackson, T. A., & Telser, J. (2016). Spectroscopic and Computational Investigation of Low-Spin Mn(III) Bis(scorpionate) Complexes. European Journal of Inorganic Chemistry, 2016(15-16), 2413–2423. http://doi.org/10.1002/ejic.201501250, which has been published in final form at 10.1002/ejic.201501250. This article may be used for non-commercial purposes in accordance with Wiley Terms and Conditions for Self-Archiving.
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    Abstract
    Six-coordinate MnIII complexes are typically high-spin (S = 2), however, the scorpionate ligand, both in its traditional, hydridotris(pyrazolyl)borate form, Tp– and Tp*– (the latter with 3,5-dimethylpyrazole substituents) and in an aryltris(carbene)borate (i.e., N-heterocyclic carbene, NHC) form, [Ph(MeIm)3B]–, (MeIm = 3-methylimidazole) lead to formation of bis(scorpionate) complexes of MnIII with spin triplet ground states; three of which were investigated herein: [Tp2Mn]SbF6 (1SbF6), [Tp*2Mn]SbF6 (2SbF6), and [{Ph(MeIm)3B}2Mn]CF3SO3 (3CF3SO3). These trigonally symmetric complexes were studied experimentally by magnetic circular dichroism (MCD) spectroscopy (the propensity of 3 to oxidize to MnIV precluded collection of useful MCD data) including variable temperatures and fields (VTVH-MCD) and computationally by ab initio CASSCF/NEVPT2 methods. These combined experimental and theoretical techniques establish the 3A2g electronic ground state for the three complexes, and provide information on the energy of the “conventional” high-spin excited state (5Eg) and other, triplet excited states. These results show the electronic effect of pyrazole ring substituents in comparing 1 and 2. The tunability of the scorpionate ligand, even by perhaps the simplest change (from pyrazole in 1 to 3,5-dimethylpyrazole in 2) is quantitatively manifested through perturbations in ligand-field excited-state energies that impact ground-state zero-field splittings. The comparison with the NHC donor is much more dramatic. In 3, the stronger σ-donor properties of the NHC lead to a quantitatively different electronic structure, so that the lowest lying spin triplet excited state, 3Eg, is much closer in energy to the ground state than in 1 or 2. The zero-field splitting (zfs) parameters of the three complexes were calculated and in the case of 1 and 2 compare closely to experiment (lower by < 10 %, < 2 cm–1 in absolute terms); for 3 the large magnitude zfs is reproduced, although there is ambiguity about its sign. The comprehensive picture obtained for these bis(scorpionate) MnIII complexes provides quantitative insight into the role played by the scorpionate ligand in stabilizing unusual electronic structures.
    URI
    http://hdl.handle.net/1808/24878
    DOI
    https://doi.org/10.1002/ejic.201501250
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    • Chemistry Scholarly Works [616]
    Citation
    Colmer, H. E., Margarit, C. G., Smith, J. M., Jackson, T. A., & Telser, J. (2016). Spectroscopic and Computational Investigation of Low-Spin Mn(III) Bis(scorpionate) Complexes. European Journal of Inorganic Chemistry, 2016(15-16), 2413–2423. http://doi.org/10.1002/ejic.201501250

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    Contact KU ScholarWorks
    785-864-8983
    KU Libraries
    1425 Jayhawk Blvd
    Lawrence, KS 66045
    785-864-8983

    KU Libraries
    1425 Jayhawk Blvd
    Lawrence, KS 66045
    Image Credits
     

     

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