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

30 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

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Iridium
Pyridine
Oxidation-Reduction
Ligands
Isomers
Oxidation
Discrete Fourier transforms
Metals
Catalysts
Water
pyridine

ASJC Scopus subject areas

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

Cite this

Stable Iridium(IV) Complexes of an Oxidation-Resistant Pyridine-Alkoxide Ligand : Highly Divergent Redox Properties Depending on the Isomeric Form Adopted. / Shopov, Dimitar Y.; Rudshteyn, Benjamin; Campos, Jesús; Batista, Victor S.; Crabtree, Robert H.; Brudvig, Gary W.

In: Journal of the American Chemical Society, Vol. 137, No. 22, 10.06.2015, p. 7243-7250.

Research output: Contribution to journalArticle

Shopov, Dimitar Y. ; Rudshteyn, Benjamin ; Campos, Jesús ; Batista, Victor S. ; Crabtree, Robert H. ; Brudvig, Gary W. / Stable Iridium(IV) Complexes of an Oxidation-Resistant Pyridine-Alkoxide Ligand : Highly Divergent Redox Properties Depending on the Isomeric Form Adopted. In: Journal of the American Chemical Society. 2015 ; Vol. 137, No. 22. pp. 7243-7250.
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