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.

doi:10.1021/jacs.5b04185

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

Journal Article · Tue May 19 00:00:00 EDT 2015 · Journal of the American Chemical Society

DOI:https://doi.org/10.1021/jacs.5b04185· OSTI ID:1385948

Shopov, Dimitar Y. ^[1]; Rudshteyn, Benjamin ^[1]; Campos, Jesús ^[1]; Batista, Victor S. ^[1]; Crabtree, Robert H. ^[1]; Brudvig, Gary W. ^[1]

Yale Univ., New Haven, CT (United States)

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 herein. The strongly donating N₃O₃ ligand set is very oxidation-resistant, yet promotes facile metal-centered oxidation to form stable Ir(IV) compounds. The Ir^III/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.

View Accepted Manuscript (DOE)

Research Organization:: Energy Frontier Research Centers (EFRC) (United States). Argonne-Northwestern Solar Energy Research Center (ANSER)

Sponsoring Organization:: USDOE Office of Science (SC), Basic Energy Sciences (BES)

Grant/Contract Number:: SC0001059

OSTI ID:: 1385948

Journal Information:: Journal of the American Chemical Society, Journal Name: Journal of the American Chemical Society Journal Issue: 22 Vol. 137; ISSN 0002-7863

Publisher:: American Chemical Society (ACS)Copyright Statement

Country of Publication:: United States

Language:: English

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Synthesis and structural characterisation of unprecedented primary N -nitrosamines coordinated to iridium( iv ) Foi, Ana; Salvo, Florencia Di; Doctorovich, Fabio Dalton Transactions, Vol. 47, Issue 33 https://doi.org/10.1039/c8dt02549e	journal	January 2018
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Copper Containing Molecular Systems in Electrocatalytic Water Oxidation—Trends and Perspectives Lukács, Dávid; Szyrwiel, Łukasz; Pap, József Catalysts, Vol. 9, Issue 1 https://doi.org/10.3390/catal9010083	journal	January 2019

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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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