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Issue 2, 2017
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A full set of iridium(IV) pyridine-alkoxide stereoisomers: highly geometry-dependent redox properties

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Abstract

We introduce and characterize the complete set of possible isomers of IrIV(pyalk)2Cl2 (pyalk = 2-(pyridin-2-yl)propan-2-oate), providing valuable insights on the properties of Ir(IV) species. The pyridine alkoxide ligand strongly stabilizes high oxidation states, essential to accessing the catalytically relevant Ir(IV) state, and results in robust complexes that can be handled under ambient conditions, even permitting chromatographic separation. The redox properties are isomer-dependent, spanning a 300 mV range, rationalized with ligand-field theory and DFT calculations. The reported complexes exhibit very high kinetic inertness against isomerization, despite highly disparate predicted thermodynamic stabilities, presenting a unique opportunity to study all five possible isomeric complexes with the same ligand set.

Graphical abstract: A full set of iridium(iv) pyridine-alkoxide stereoisomers: highly geometry-dependent redox properties

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Publication details

The article was received on 21 Aug 2016, accepted on 06 Nov 2016 and first published on 07 Nov 2016


Article type: Edge Article
DOI: 10.1039/C6SC03758E
Citation: Chem. Sci., 2017,8, 1642-1652
  • Open access: Creative Commons BY-NC license
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    A full set of iridium(IV) pyridine-alkoxide stereoisomers: highly geometry-dependent redox properties

    D. Y. Shopov, B. Rudshteyn, J. Campos, D. J. Vinyard, V. S. Batista, G. W. Brudvig and R. H. Crabtree, Chem. Sci., 2017, 8, 1642
    DOI: 10.1039/C6SC03758E

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