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

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9 Scopus citations


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
Issue number20
StatePublished - Apr 6 2018

Bibliographical note

Funding Information:
J.E.M.N.K. thanks the Alexander von Humboldt Foundation for a Feodor Lynen Research Fellowship. For support of this work, we thank the National Science Foundation (CHE-1361595 to C.J.C., and CHE-1231085 to L.Q.). The authors acknowledge the Minnesota Supercomputing Institute (MSI) at the University of Minnesota for providing resources that contributed to the research results reported within this paper. We would also like to thank the Center for Information Technology of the University of Groningen for their support and for providing access to the Peregrine high performance computing cluster.

Publisher Copyright:
© 2018 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim


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


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