Structural implications of the paramagnetically shifted NMR signals from pyridine H atoms on synthetic nonheme FeIV=O complexes

Waqas Rasheed, Ruixi Fan, Chase S. Abelson, Paul O. Peterson, Wei-Min Ching, Yisong Guo, Larry Que

Research output: Contribution to journalArticle

Abstract

Oxoiron(IV) motifs are found in important intermediates in many enzymatic cycles that involve oxidations. Over half of the reported synthetic nonheme oxoiron(IV) analogs incorporate heterocyclic donors, with a majority of them comprising pyridines. Herein, we report 1H-NMR studies of oxoiron(IV) complexes containing pyridines that are arranged in different configurations relative to the Fe = O unit and give rise to paramagnetically shifted resonances that differ by as much as 50 ppm. The strong dependence of 1H-NMR shifts on the different configurations and orientation of pyridines relative to the oxoiron(IV) unit demonstrates how unpaired electronic spin density of the iron center affects the chemical shifts of these protons.

Original languageEnglish (US)
Pages (from-to)533-545
Number of pages13
JournalJournal of Biological Inorganic Chemistry
Volume24
Issue number4
DOIs
StatePublished - Jun 1 2019

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Pyridines
Nuclear magnetic resonance
Atoms
Chemical shift
Protons
Iron
Oxidation
pyridine
Proton Magnetic Resonance Spectroscopy

Keywords

  • Iron(IV)-oxo complexes
  • NMR
  • Nonheme iron

Cite this

Structural implications of the paramagnetically shifted NMR signals from pyridine H atoms on synthetic nonheme FeIV=O complexes. / Rasheed, Waqas; Fan, Ruixi; Abelson, Chase S.; Peterson, Paul O.; Ching, Wei-Min; Guo, Yisong; Que, Larry.

In: Journal of Biological Inorganic Chemistry, Vol. 24, No. 4, 01.06.2019, p. 533-545.

Research output: Contribution to journalArticle

Rasheed, Waqas ; Fan, Ruixi ; Abelson, Chase S. ; Peterson, Paul O. ; Ching, Wei-Min ; Guo, Yisong ; Que, Larry. / Structural implications of the paramagnetically shifted NMR signals from pyridine H atoms on synthetic nonheme FeIV=O complexes. In: Journal of Biological Inorganic Chemistry. 2019 ; Vol. 24, No. 4. pp. 533-545.
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