title: Stable Iridium(IV) Complexes of an Oxidation-Resistant Pyridine-Alkoxide Ligand: Highly Divergent Redox Properties Depending on the Isomeric Form Adopted.
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 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.
authors.affiliation: Department of Chemistry, Yale University, New Haven, Connecticut 06520, United States.
authors.forename: Dimitar Y
authors.initials: DY
authors.lastname: Shopov
authors.affiliation: Department of Chemistry, Yale University, New Haven, Connecticut 06520, United States.
authors.forename: Benjamin
authors.initials: B
authors.lastname: Rudshteyn
authors.affiliation: Department of Chemistry, Yale University, New Haven, Connecticut 06520, United States.
authors.forename: Jesús
authors.initials: J
authors.lastname: Campos
authors.affiliation: Department of Chemistry, Yale University, New Haven, Connecticut 06520, United States.
authors.forename: Victor S
authors.initials: VS
authors.lastname: Batista
authors.affiliation: Department of Chemistry, Yale University, New Haven, Connecticut 06520, United States.
authors.forename: Robert H
authors.initials: RH
authors.lastname: Crabtree
authors.affiliation: Department of Chemistry, Yale University, New Haven, Connecticut 06520, United States.
authors.forename: Gary W
authors.initials: GW
authors.lastname: Brudvig