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

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Department of Chemistry, Yale University, New Haven, Connecticut 06520, United States
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*[email protected]
Cite this: J. Am. Chem. Soc. 2015, 137, 22, 7243–7250
Publication Date (Web):May 19, 2015
https://doi.org/10.1021/jacs.5b04185
Copyright © 2015 American Chemical Society
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    Abstract

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    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.

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    Structural data files and detailed crystallographic information, as well as additional experimental data are provided. The Supporting Information is available free of charge on the ACS Publications website at DOI: 10.1021/jacs.5b04185.

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