Nonheme Fe(IV) Oxo Complexes of Two New Pentadentate Ligands and Their Hydrogen-Atom and Oxygen-Atom Transfer Reactions

Research output: Contribution to journalArticle


Two new pentadentate {N5} donor ligands based on the N4Py (N4Py = N,N-bis(2-pyridylmethyl)-N-bis(2-pyridyl)methylamine) framework have been synthesized, viz. [N-(1-methyl-2-benzimidazolyl)methyl-N-(2-pyridyl)methyl-N-(bis-2-pyridyl methyl)amine] (L1) and [N-bis(1-methyl-2-benzimidazolyl)methyl-N-(bis-2-pyridylmethyl)amine] (L2), where one or two pyridyl arms of N4Py have been replaced by corresponding (N-methyl)benzimidazolyl-containing arms. The complexes [FeII(CH3CN)(L)]2+ (L = L1 (1); L2 (2)) were synthesized, and reaction of these ferrous complexes with iodosylbenzene led to the formation of the ferryl complexes [FeIV(O)(L)]2+ (L = L1 (3); L2 (4)), which were characterized by UV–vis spectroscopy, high resolution mass spectrometry, and Mössbauer spectroscopy. Complexes 3 and 4 are relatively stable with half-lives at room temperature of 40 h (L = L1) and 2.5 h (L = L2). The redox potentials of 1 and 2, as well as the visible spectra of 3 and 4, indicate that the ligand field weakens as ligand pyridyl substituents are progressively substituted by (N-methyl)benzimidazolyl moieties. The reactivities of 3 and 4 in hydrogen-atom transfer (HAT) and oxygen-atom transfer (OAT) reactions show that both complexes exhibit enhanced reactivities when compared to the analogous N4Py complex ([FeIV(O)(N4Py)]2+), and that the normalized HAT rates increase by approximately 1 order of magnitude for each replacement of a pyridyl moiety; i.e., [FeIV(O)(L2)]2+ exhibits the highest rates. The second-order HAT rate constants can be directly related to the substrate C–H bond dissociation energies. Computational modeling of the HAT reactions indicates that the reaction proceeds via a high spin transition state.


  • Mainak Mitra
  • Hassan Nimir
  • Serhiy Demeshko
  • Satish Bhat
  • Sergey O. Malinkin
  • Matti Haukka
  • Julio Lloret-Fillol
  • George C. Lisensky
  • Franc Meyer
  • Albert A. Shteinman
  • Wesley R. Browne
  • David A. Hrovat
  • Michael G. Richmond
  • Miquel Costas
  • Ebbe Nordlander
Research areas and keywords

Subject classification (UKÄ) – MANDATORY

  • Inorganic Chemistry
Original languageEnglish
Pages (from-to)7152-7164
JournalInorganic Chemistry
Issue number15
Publication statusPublished - 2015
Publication categoryResearch

Bibliographic note

The information about affiliations in this record was updated in December 2015. The record was previously connected to the following departments: Chemical Physics (S) (011001060), External organization(s) (LUR000040)