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Long GJ, Grandjean F, Harrop TC, et al. Combined Mössbauer Spectral and Density Functional Study of an Eight-Coordinate Iron(II) Complex. Inorg Chem. 2015;54(17):8415-22doi: 10.1021/acs.inorgchem.5b01121.
Long, G. J., Grandjean, F., Harrop, T. C., Petroccia, H. M., & Papaefthymiou, G. C. (2015). Combined Mössbauer Spectral and Density Functional Study of an Eight-Coordinate Iron(II) Complex. Inorganic chemistry, 54(17), 8415-22. https://doi.org/10.1021/acs.inorgchem.5b01121
Long, Gary J, et al. "Combined Mössbauer Spectral and Density Functional Study of an Eight-Coordinate Iron(II) Complex." Inorganic chemistry vol. 54,17 (2015): 8415-22. doi: https://doi.org/10.1021/acs.inorgchem.5b01121
Long GJ, Grandjean F, Harrop TC, Petroccia HM, Papaefthymiou GC. Combined Mössbauer Spectral and Density Functional Study of an Eight-Coordinate Iron(II) Complex. Inorg Chem. 2015 Sep 08;54(17):8415-22. doi: 10.1021/acs.inorgchem.5b01121. Epub 2015 Aug 12. PMID: 26267610.
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Inorg Chem. 2015 Sep 08;54(17):8415-22. doi: 10.1021/acs.inorgchem.5b01121. Epub 2015 Aug 12.

Combined Mössbauer Spectral and Density Functional Study of an Eight-Coordinate Iron(II) Complex.

Inorganic chemistry

Gary J Long, Fernande Grandjean, Todd C Harrop, Heather M Petroccia, Georgia C Papaefthymiou

Affiliations

  1. Department of Chemistry, Missouri University of Science and Technology, University of Missouri , Rolla, Missouri 65409-0010, United States.
  2. Department of Chemistry, The University of Georgia , Athens, Georgia 30602, United States.
  3. Department of Physics, Villanova University , Villanova, Pennsylvania 19085, United States.

PMID: 26267610 DOI: 10.1021/acs.inorgchem.5b01121

Abstract

The iron-57 Mössbauer spectra of the eight-coordinate complex, [Fe(L(N4))2](BF4)2, where L(N4) is the tetradentate N(1)(E),N(2)(E)-bis[(1-methyl-1H-imidazol-2-yl)methylene]-1,2-benzenediimine ligand, have been measured between 4.2 and 295 K and fit with a quadrupole doublet. The fit at 4.2 K yields an isomer shift, δ(Fe), of 1.260(1) mm/s and a quadrupole splitting, ΔE(Q), of 3.854(2) mm/s, values that are typical of a high-spin iron(II) complex. The temperature dependence of the isomer shift yields a Mössbauer temperature, Θ(M), of 319(27) K and the temperature dependence of the logarithm of the Mössbauer spectral absorption area yields a Debye temperature, Θ(D), of 131(6) K, values that are indicative of high-spin iron(II). Nonrelativistic single point density functional calculations with the B3LYP functional, the full 6-311++G(d,p) basis set, and the known X-ray structures for [Mn(L(N4))2](2+), [Mn(L(N4))2](ClO4)2, 1, [Fe(L(N4))2](2+), and [Fe(L(N4))2](BF4)2, 2, yield small electric field gradients for the manganese(II) complexes and electric field gradients and s-electron densities at the iron-57 nuclide that are in good to excellent agreement with the Mössbauer spectral parameters. The structure of 2 with a distorted square-antiprism C1 iron(II) coordination symmetry exhibits four different Fe-N(imid) bonds to the imidazole nitrogens with an average bond distance of 2.253(2) Å and four different Fe-N(imine) bonds to the benzenediimine nitrogens, with an average bond distance of 2.432(2) Å; this large difference yields the large observed ΔE(Q). An optimization of the [Fe(L(N4))2](2+) structure leads to a highly symmetric eight-coordination environment with S4 symmetry and four equivalent Fe-N(imid) bond distances of 2.301(2) Å and four equivalent Fe-N(imine) bond distances of 2.487(2) Å. In contrast, an optimization of the [Mn(LN4)2](2+) structure leads to an eight-coordination manganese(II) environment with D(2d) symmetry and four equivalent Mn-N(imid) bond distances of 2.350(3) Å and four equivalent Mn-N(imine) bond distances of 2.565(3) Å.

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