A Bispidine Iron(IV)–Oxo Complex in the Entatic State

Peter Comba, Shunichi Fukuzumi, Carsten Koke, Bodo Martin, Anna Maria Löhr, Johannes Straub

Research output: Contribution to journalArticlepeer-review

41 Scopus citations

Abstract

For a series of FeIV=O complexes with tetra- and pentadentate bispidine ligands, the correlation of their redox potentials with reactivity, involving a variety of substrates for alkane hydroxylation (HAT), alkene epoxidation, and phosphine and thioether oxidation (OAT) are reported. The redox potentials span approximately 350 mV and the reaction rates over 8 orders of magnitude. From the experimental data and in comparison with published studies it emerges that electron transfer and the driving force are of major importance, and this is also supported by the DFT-based computational analysis. The striking difference of reactivity of two isomeric systems with pentadentate bispidines is found to be due to a destabilization of the S=1 ground state of one of the ferryl isomers, and this is supported by the experimentally determined redox potentials and published stability constants with a series of first-row transition metal ions with these two isomeric ligands.

Original languageEnglish
Pages (from-to)11129-11133
Number of pages5
JournalAngewandte Chemie - International Edition
Volume55
Issue number37
DOIs
StatePublished - 5 Sep 2016

Bibliographical note

Publisher Copyright:
© 2016 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim

Keywords

  • coordination chemistry
  • density functional calculations
  • homogeneous catalysis
  • iron bispidine complexes
  • redox potentials

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