Synthesis and Characterization of Iridium(V) Coordination Complexes With an N,O-Donor Organic Ligand

Sharninghausen, Liam S.; Sinha, Shashi Bhushan; Shopov, Dimitar Y.; Mercado, Brandon Q.; Balcells, David; Brudvig, Gary W.; Crabtree, Robert H.

doi:10.1002/anie.201707593

Synthesis and Characterization of Iridium(V) Coordination Complexes With an N,O-Donor Organic Ligand

Journal Article · Wed Aug 16 00:00:00 EDT 2017 · Angewandte Chemie (International Edition)

DOI:https://doi.org/10.1002/anie.201707593· OSTI ID:1470376

^[1]; ^[1]; Shopov, Dimitar Y. ^[1]; Mercado, Brandon Q. ^[1]; Balcells, David ^[2]; Brudvig, Gary W. ^[1]; ^[1]

Yale Univ., New Haven, CT (United States)
Univ. of Oslo (Norway)

Here, we have prepared and fully characterized two isomers of [IrI^V(dpyp)₂] (dpyp=meso-2,4-di(2-pyridinyl)-2,4-pentanediolate). These complexes can cleanly oxidize to [Ir^V(dpyp)₂]⁺, which to our knowledge represent the first mononuclear coordination complexes of Ir^V in an N,O-donor environment. One isomer has been fully characterized in the Ir^V state, including by X-ray crystallography, XPS, and DFT calculations, all of which validate metal-centered oxidation. The unprecedented stability of these Ir^V complexes is ascribed to the exceptional donor strength of the ligands, their resistance to oxidative degradation, and the presence of four highly donor alkoxide groups in a plane, which breaks the degeneracy of the d-orbitals and favors oxidation.

View Accepted Manuscript (DOE)

Research Organization:: Northwestern Univ., Evanston, IL (United States). Energy Frontier Research Center (EFRC) Argonne-Northwestern Solar Energy Research Center (ANSER); Yale Univ., New Haven, CT (United States)

Sponsoring Organization:: Research Council of Norway; USDOE Office of Science (SC), Basic Energy Sciences (BES) (SC-22)

Grant/Contract Number:: FG02-07ER15909; SC0001059

OSTI ID:: 1470376

Alternate ID(s):: OSTI ID: 1378790

Journal Information:: Angewandte Chemie (International Edition), Journal Name: Angewandte Chemie (International Edition) Journal Issue: 42 Vol. 56; ISSN 1433-7851

Publisher:: WileyCopyright Statement

Country of Publication:: United States

Language:: English

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Hydroxyl Group-Prompted and Iridium(III)-Catalyzed Regioselective C−H Annulation of N -phenoxyacetamides with Propargyl Alcohols Chen, Weijie; Liu, Fu-Xiaomin; Gong, Wanchun Advanced Synthesis & Catalysis, Vol. 360, Issue 13 https://doi.org/10.1002/adsc.201800322	journal	May 2018
Electrochemical and Kinetic Insights into Molecular Water Oxidation Catalysts Derived from Cp*Ir(pyridine‐alkoxide) Complexes Sackville, Emma V.; Marken, Frank; Hintermair, Ulrich ChemCatChem, Vol. 10, Issue 19 https://doi.org/10.1002/cctc.201800916	journal	August 2018
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CCDC 1562806: Experimental Crystal Structure Determination Sharninghausen, Liam S.; Sinha, Shashi Bhushan; Shopov, Dimitar Y. https://doi.org/10.5517/ccdc.csd.cc1pg73h The current record is supplemented by this dataset	dataset	January 2017
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Synthesis and Characterization of Iridium(V) Coordination Complexes With an N,O-Donor Organic Ligand

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