NMR Reveals That a Highly Reactive Nonheme FeIV=O Complex Retains Its Six-Coordinate Geometry and S=1 State in Solution

Saikat Banerjee, Waqas Rasheed, Ruixi Fan, Apparao Draksharapu, Williamson N. Oloo, Yisong Guo, Larry Que

Research output: Contribution to journalArticle

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Abstract

The [FeIV(O)(Me3NTB)]2+ (Me3NTB=tris[(1-methyl-benzimidazol-2-yl)methyl]amine) complex 1 has been shown by Mössbauer spectroscopy to have an S=1 ground state at 4 K, but is proposed to become an S=2 trigonal-bipyramidal species at higher temperatures based on a DFT model to rationalize its very high C−H bond-cleavage reactivity. In this work, 1H NMR spectroscopy was used to determine that 1 does not have C3-symmetry in solution and is not an S=2 species. Our results show that 1 is unique among nonheme FeIV=O complexes in retaining its S=1 spin state and high reactivity at 193 K, providing evidence that S=1 FeIV=O complexes can be as reactive as their S=2 counterparts. This result emphasizes the need to identify factors besides the ground spin state of the FeIV=O center to rationalize nonheme oxoiron(IV) reactivity.

Original languageEnglish (US)
Pages (from-to)9608-9613
Number of pages6
JournalChemistry - A European Journal
Volume25
Issue number41
DOIs
StatePublished - Jul 22 2019

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Discrete Fourier transforms
Ground state
Nuclear magnetic resonance spectroscopy
Amines
Nuclear magnetic resonance
Spectroscopy
Geometry
Temperature

Keywords

  • DFT calculations
  • NMR spectroscopy
  • nonheme iron
  • oxoiron(IV) complexes
  • two-state reactivity

PubMed: MeSH publication types

  • Journal Article

Cite this

NMR Reveals That a Highly Reactive Nonheme FeIV=O Complex Retains Its Six-Coordinate Geometry and S=1 State in Solution. / Banerjee, Saikat; Rasheed, Waqas; Fan, Ruixi; Draksharapu, Apparao; Oloo, Williamson N.; Guo, Yisong; Que, Larry.

In: Chemistry - A European Journal, Vol. 25, No. 41, 22.07.2019, p. 9608-9613.

Research output: Contribution to journalArticle

Banerjee, Saikat ; Rasheed, Waqas ; Fan, Ruixi ; Draksharapu, Apparao ; Oloo, Williamson N. ; Guo, Yisong ; Que, Larry. / NMR Reveals That a Highly Reactive Nonheme FeIV=O Complex Retains Its Six-Coordinate Geometry and S=1 State in Solution. In: Chemistry - A European Journal. 2019 ; Vol. 25, No. 41. pp. 9608-9613.
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