A Dimeric Hydride-Bridged Complex with Geometrically Distinct Iron Centers Giving Rise to an S = 3 Ground State

Anne K. Hickey, Samuel M. Greer, Juan A. Valdez-Moreira, Sean A. Lutz, Maren Pink, Jordan A. Degayner, Thomas David Harris, Stephen Hill, Joshua Telser, Jeremy M. Smith*

*Corresponding author for this work

Research output: Contribution to journalArticle

Abstract

Structural and spectroscopic characterization of the dimeric iron hydride complex [Ph2B(tBuIm)2FeH]2 reveals an unusual structure in which a tetrahedral iron(II) site (S = 2) is connected to a square planar iron(II) site (S = 1) by two bridging hydride ligands. Magnetic susceptibility reveals strong ferromagnetic coupling between iron centers, with a coupling constant of J = +110(12) cm-1, to give an S = 3 ground state. High-frequency and -field electron paramagnetic resonance (HFEPR) spectroscopy confirms this model. A qualitative molecular orbital analysis of the electronic structure, as supported by electronic structure calculations, reveals that the observed spin configuration results from the orthogonal alignment of two geometrically distinct four-coordinate iron fragments held together by highly covalent hydride ligands.

Original languageEnglish (US)
Pages (from-to)11970-11975
Number of pages6
JournalJournal of the American Chemical Society
Volume141
Issue number30
DOIs
StatePublished - Jul 31 2019

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Hydrides
Ground state
Iron
Electronic structure
Ligands
Electron Spin Resonance Spectroscopy
Molecular orbitals
Magnetic susceptibility
Paramagnetic resonance
Spectrum Analysis
Spectroscopy

ASJC Scopus subject areas

  • Catalysis
  • Chemistry(all)
  • Biochemistry
  • Colloid and Surface Chemistry

Cite this

Hickey, A. K., Greer, S. M., Valdez-Moreira, J. A., Lutz, S. A., Pink, M., Degayner, J. A., ... Smith, J. M. (2019). A Dimeric Hydride-Bridged Complex with Geometrically Distinct Iron Centers Giving Rise to an S = 3 Ground State. Journal of the American Chemical Society, 141(30), 11970-11975. https://doi.org/10.1021/jacs.9b04389
Hickey, Anne K. ; Greer, Samuel M. ; Valdez-Moreira, Juan A. ; Lutz, Sean A. ; Pink, Maren ; Degayner, Jordan A. ; Harris, Thomas David ; Hill, Stephen ; Telser, Joshua ; Smith, Jeremy M. / A Dimeric Hydride-Bridged Complex with Geometrically Distinct Iron Centers Giving Rise to an S = 3 Ground State. In: Journal of the American Chemical Society. 2019 ; Vol. 141, No. 30. pp. 11970-11975.
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abstract = "Structural and spectroscopic characterization of the dimeric iron hydride complex [Ph2B(tBuIm)2FeH]2 reveals an unusual structure in which a tetrahedral iron(II) site (S = 2) is connected to a square planar iron(II) site (S = 1) by two bridging hydride ligands. Magnetic susceptibility reveals strong ferromagnetic coupling between iron centers, with a coupling constant of J = +110(12) cm-1, to give an S = 3 ground state. High-frequency and -field electron paramagnetic resonance (HFEPR) spectroscopy confirms this model. A qualitative molecular orbital analysis of the electronic structure, as supported by electronic structure calculations, reveals that the observed spin configuration results from the orthogonal alignment of two geometrically distinct four-coordinate iron fragments held together by highly covalent hydride ligands.",
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Hickey, AK, Greer, SM, Valdez-Moreira, JA, Lutz, SA, Pink, M, Degayner, JA, Harris, TD, Hill, S, Telser, J & Smith, JM 2019, 'A Dimeric Hydride-Bridged Complex with Geometrically Distinct Iron Centers Giving Rise to an S = 3 Ground State', Journal of the American Chemical Society, vol. 141, no. 30, pp. 11970-11975. https://doi.org/10.1021/jacs.9b04389

A Dimeric Hydride-Bridged Complex with Geometrically Distinct Iron Centers Giving Rise to an S = 3 Ground State. / Hickey, Anne K.; Greer, Samuel M.; Valdez-Moreira, Juan A.; Lutz, Sean A.; Pink, Maren; Degayner, Jordan A.; Harris, Thomas David; Hill, Stephen; Telser, Joshua; Smith, Jeremy M.

In: Journal of the American Chemical Society, Vol. 141, No. 30, 31.07.2019, p. 11970-11975.

Research output: Contribution to journalArticle

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AU - Hickey, Anne K.

AU - Greer, Samuel M.

AU - Valdez-Moreira, Juan A.

AU - Lutz, Sean A.

AU - Pink, Maren

AU - Degayner, Jordan A.

AU - Harris, Thomas David

AU - Hill, Stephen

AU - Telser, Joshua

AU - Smith, Jeremy M.

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