Stable Iridium(IV) Complexes of an Oxidation-Resistant Pyridine-Alkoxide Ligand: Highly Divergent Redox Properties Depending on the Isomeric Form Adopted

Dimitar Y. Shopov, Benjamin Rudshteyn, Jesús Campos, Victor S. Batista, Robert H. Crabtree, Gary W. Brudvig

Research output: Contribution to journalArticle

31 Citations (Scopus)

Abstract

The preparation of the facial and meridional isomers of [Ir(pyalk)3] (pyalk = 2-(2-pyridyl)isopropanoate), as model complexes for a powerful water oxidation catalyst, is reported. The strongly donating N3O3 ligand set is very oxidation-resistant, yet promotes facile metal-centered oxidation to form stable Ir(IV) compounds. The IrIII/IV reduction potentials of the two isomers differ by 340 mV despite the identical ligand set. A ligand field rationalization is advanced and supported by DFT calculations. (Chemical Equation Presented).

Original languageEnglish
Pages (from-to)7243-7250
Number of pages8
JournalJournal of the American Chemical Society
Volume137
Issue number22
DOIs
Publication statusPublished - Jun 10 2015

ASJC Scopus subject areas

  • Catalysis
  • Chemistry(all)
  • Biochemistry
  • Colloid and Surface Chemistry

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