On the Lewis Acidity of the Oxoiron(IV) Unit in a Tetramethylcyclam Complex

Johannes E.M.N. Klein, Apparao Draksharapu, Alireza Shokri, Chris Cramer, Larry Que

Research output: Contribution to journalArticle

3 Citations (Scopus)

Abstract

The correlation between oxidation state and Lewis acidity is well established for hexaquairon complexes in the +II and +III oxidation state, in which the higher oxidation state leads to a lower pKa for the bound H2O ligand. This article addresses the Lewis acidity of the oxoiron(IV) complex [FeIV(O)(TMC)(OH2)]2+ (1-OH2; TMC=1,4,8,11-tetramethylcyclam) by determining the pKa of the H2O ligand. We establish that 1-OH2 has a pKa of 6.9±0.5, a value that falls in between those found for [FeIII(OH2)6]3+ and [FeII(OH2)6]2+. This intermediate value can be readily rationalized by the presence of the highly basic oxide ligand that mitigates the Lewis acidity of the iron(IV) center. Although the oxo ligand occupies only one position in 1-OH2, anti to all four methyl groups that protrude from the same face of the nonplanar TMC ligand, its conjugate base 1-OH exists as a mixture of syn and anti tautomers, which are related by proton transfer between the oxo and the hydroxo ligands.

Original languageEnglish (US)
Pages (from-to)5373-5378
Number of pages6
JournalChemistry - A European Journal
Volume24
Issue number20
DOIs
StatePublished - Apr 6 2018

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Acidity
Ligands
Oxidation
Proton transfer
Oxides
Iron

Keywords

  • Lewis acids
  • acidity
  • iron
  • oxoiron(IV) complexes
  • tetramethylcyclam

PubMed: MeSH publication types

  • Journal Article

Cite this

On the Lewis Acidity of the Oxoiron(IV) Unit in a Tetramethylcyclam Complex. / Klein, Johannes E.M.N.; Draksharapu, Apparao; Shokri, Alireza; Cramer, Chris; Que, Larry.

In: Chemistry - A European Journal, Vol. 24, No. 20, 06.04.2018, p. 5373-5378.

Research output: Contribution to journalArticle

Klein, Johannes E.M.N. ; Draksharapu, Apparao ; Shokri, Alireza ; Cramer, Chris ; Que, Larry. / On the Lewis Acidity of the Oxoiron(IV) Unit in a Tetramethylcyclam Complex. In: Chemistry - A European Journal. 2018 ; Vol. 24, No. 20. pp. 5373-5378.
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