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

Abstract

Here, we have prepared and fully characterized two isomers of [IrIV(dpyp)2] (dpyp=meso-2,4-di(2-pyridinyl)-2,4-pentanediolate). These complexes can cleanly oxidize to [IrV(dpyp)2]+, which to our knowledge represent the first mononuclear coordination complexes of IrV in an N,O-donor environment. One isomer has been fully characterized in the IrV state, including by X-ray crystallography, XPS, and DFT calculations, all of which validate metal-centered oxidation. The unprecedented stability of these IrV 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.

Authors:
ORCiD logo [1]; ORCiD logo [1];  [1];  [1];  [2];  [1]; ORCiD logo [1]
  1. Yale Univ., New Haven, CT (United States)
  2. Univ. of Oslo (Norway)
Publication Date:
Research Org.:
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 Org.:
USDOE Office of Science (SC), Basic Energy Sciences (BES); Research Council of Norway
OSTI Identifier:
1470376
Alternate Identifier(s):
OSTI ID: 1378790
Grant/Contract Number:  
SC0001059; FG02-07ER15909
Resource Type:
Accepted Manuscript
Journal Name:
Angewandte Chemie (International Edition)
Additional Journal Information:
Journal Name: Angewandte Chemie (International Edition); Journal Volume: 56; Journal Issue: 42; Related Information: ANSER partners with Northwestern University (lead); Argonne National Laboratory; University of Chicago; University of Illinois, Urbana-Champaign; Yale University; Journal ID: ISSN 1433-7851
Publisher:
Wiley
Country of Publication:
United States
Language:
English
Subject:
37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY; alkoxide ligands; computational chemistry; high oxidation state; iridium(V); redox chemistry

Citation Formats

Sharninghausen, Liam S., Sinha, Shashi Bhushan, Shopov, Dimitar Y., Mercado, Brandon Q., Balcells, David, Brudvig, Gary W., and Crabtree, Robert H. Synthesis and Characterization of Iridium(V) Coordination Complexes With an N,O-Donor Organic Ligand. United States: N. p., 2017. Web. doi:10.1002/anie.201707593.
Sharninghausen, Liam S., Sinha, Shashi Bhushan, Shopov, Dimitar Y., Mercado, Brandon Q., Balcells, David, Brudvig, Gary W., & Crabtree, Robert H. Synthesis and Characterization of Iridium(V) Coordination Complexes With an N,O-Donor Organic Ligand. United States. doi:10.1002/anie.201707593.
Sharninghausen, Liam S., Sinha, Shashi Bhushan, Shopov, Dimitar Y., Mercado, Brandon Q., Balcells, David, Brudvig, Gary W., and Crabtree, Robert H. Wed . "Synthesis and Characterization of Iridium(V) Coordination Complexes With an N,O-Donor Organic Ligand". United States. doi:10.1002/anie.201707593. https://www.osti.gov/servlets/purl/1470376.
@article{osti_1470376,
title = {Synthesis and Characterization of Iridium(V) Coordination Complexes With an N,O-Donor Organic Ligand},
author = {Sharninghausen, Liam S. and Sinha, Shashi Bhushan and Shopov, Dimitar Y. and Mercado, Brandon Q. and Balcells, David and Brudvig, Gary W. and Crabtree, Robert H.},
abstractNote = {Here, we have prepared and fully characterized two isomers of [IrIV(dpyp)2] (dpyp=meso-2,4-di(2-pyridinyl)-2,4-pentanediolate). These complexes can cleanly oxidize to [IrV(dpyp)2]+, which to our knowledge represent the first mononuclear coordination complexes of IrV in an N,O-donor environment. One isomer has been fully characterized in the IrV state, including by X-ray crystallography, XPS, and DFT calculations, all of which validate metal-centered oxidation. The unprecedented stability of these IrV 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.},
doi = {10.1002/anie.201707593},
journal = {Angewandte Chemie (International Edition)},
number = 42,
volume = 56,
place = {United States},
year = {2017},
month = {8}
}

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Cited by: 6 works
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Works referenced in this record:

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    Works referencing / citing this record:

    Hydroxyl Group-Prompted and Iridium(III)-Catalyzed Regioselective C−H Annulation of N -phenoxyacetamides with Propargyl Alcohols
    journal, May 2018

    • Chen, Weijie; Liu, Fu-Xiaomin; Gong, Wanchun
    • Advanced Synthesis & Catalysis, Vol. 360, Issue 13
    • DOI: 10.1002/adsc.201800322

    In Situ Observation of Surface Species on Iridium Oxide Nanoparticles during the Oxygen Evolution Reaction
    journal, May 2014

    • Sanchez Casalongue, Hernan G.; Ng, May Ling; Kaya, Sarp
    • Angewandte Chemie, Vol. 126, Issue 28
    • DOI: 10.1002/ange.201402311

    Electronic Structure of Copper Corroles
    journal, January 2016

    • Lemon, Christopher M.; Huynh, Michael; Maher, Andrew G.
    • Angewandte Chemie, Vol. 128, Issue 6
    • DOI: 10.1002/ange.201509099

    In Situ Observation of Surface Species on Iridium Oxide Nanoparticles during the Oxygen Evolution Reaction
    journal, May 2014

    • Sanchez Casalongue, Hernan G.; Ng, May Ling; Kaya, Sarp
    • Angewandte Chemie International Edition, Vol. 53, Issue 28
    • DOI: 10.1002/anie.201402311

    Electronic Structure of Copper Corroles
    journal, January 2016

    • Lemon, Christopher M.; Huynh, Michael; Maher, Andrew G.
    • Angewandte Chemie International Edition, Vol. 55, Issue 6
    • DOI: 10.1002/anie.201509099

    A Stable Iridium(IV) Complex Containing the Kläui Tripodal Ligand [Co(η5-C5H5){P(O)(OEt)2}3]-
    journal, May 2012

    • Ip, Ho-Fai; So, Yat-Ming; Lee, Hung Kay
    • European Journal of Inorganic Chemistry, Vol. 2012, Issue 20
    • DOI: 10.1002/ejic.201200138

    The chemistry of ruthenium, osmium, rhodium, iridium, palladium and platinum in the higher oxidation states
    journal, October 1982


    Utilizing the Evans method with a superconducting NMR spectrometer in the undergraduate laboratory
    journal, January 1992

    • Schubert, Ernest M.
    • Journal of Chemical Education, Vol. 69, Issue 1
    • DOI: 10.1021/ed069p62.1

    Gas-Phase Molecular Structures of Third Row Transition-Metal Hexafluorides WF 6 , ReF 6 , OsF 6 , IrF 6 , and PtF 6 . An Electron-Diffraction and ab Initio Study
    journal, June 2000

    • Richardson, Alan D.; Hedberg, Kenneth; Lucier, George M.
    • Inorganic Chemistry, Vol. 39, Issue 13
    • DOI: 10.1021/ic000003c

    Seven-Coordinate Iridium(V) Polyhydrides with Chelating Bis(silyl) Ligands
    journal, May 1995

    • Loza, Maria; Faller, J. W.; Crabtree, Robert H.
    • Inorganic Chemistry, Vol. 34, Issue 11
    • DOI: 10.1021/ic00115a022

    Evaluation of Donor and Steric Properties of Anionic Ligands on High Valent Transition Metals
    journal, December 2011

    • DiFranco, Stephen A.; Maciulis, Nicholas A.; Staples, Richard J.
    • Inorganic Chemistry, Vol. 51, Issue 2
    • DOI: 10.1021/ic202524r

    Mechanism of the Mild Functionalization of Arenes by Diboron Reagents Catalyzed by Iridium Complexes. Intermediacy and Chemistry of Bipyridine-Ligated Iridium Trisboryl Complexes
    journal, October 2005

    • Boller, Timothy M.; Murphy, Jaclyn M.; Hapke, Marko
    • Journal of the American Chemical Society, Vol. 127, Issue 41
    • DOI: 10.1021/ja053433g

    Rapid C–H Bond Activation by a Monocopper(III)–Hydroxide Complex
    journal, November 2011

    • Donoghue, Patrick J.; Tehranchi, Jacqui; Cramer, Christopher J.
    • Journal of the American Chemical Society, Vol. 133, Issue 44
    • DOI: 10.1021/ja207882h

    Stabilization of Iridium(IV) by Monoanionic Dialkyldiarylguanidinato Ligands
    journal, July 2009

    • Rohde, Jan-Uwe; Lee, Wei-Tsung
    • Journal of the American Chemical Society, Vol. 131, Issue 26
    • DOI: 10.1021/ja9033445

    Stable Iridium(IV) Complexes of an Oxidation-Resistant Pyridine-Alkoxide Ligand: Highly Divergent Redox Properties Depending on the Isomeric Form Adopted
    journal, June 2015

    • Shopov, Dimitar Y.; Rudshteyn, Benjamin; Campos, Jesús
    • Journal of the American Chemical Society, Vol. 137, Issue 22
    • DOI: 10.1021/jacs.5b04185

    A Stable Coordination Complex of Rh(IV) in an N,O-Donor Environment
    journal, December 2015

    • Sinha, Shashi B.; Shopov, Dimitar Y.; Sharninghausen, Liam S.
    • Journal of the American Chemical Society, Vol. 137, Issue 50
    • DOI: 10.1021/jacs.5b12148

    Solution Structures of Highly Active Molecular Ir Water-Oxidation Catalysts from Density Functional Theory Combined with High-Energy X-ray Scattering and EXAFS Spectroscopy
    journal, April 2016

    • Yang, Ke R.; Matula, Adam J.; Kwon, Gihan
    • Journal of the American Chemical Society, Vol. 138, Issue 17
    • DOI: 10.1021/jacs.6b01750

    High Oxidation State Iridium Mono-μ-oxo Dimers Related to Water Oxidation Catalysis
    journal, December 2016

    • Sharninghausen, Liam S.; Sinha, Shashi Bhushan; Shopov, Dimitar Y.
    • Journal of the American Chemical Society, Vol. 138, Issue 49
    • DOI: 10.1021/jacs.6b07716

    Redox Activity of Oxo-Bridged Iridium Dimers in an N,O-Donor Environment: Characterization of Remarkably Stable Ir(IV,V) Complexes
    journal, July 2017

    • Sinha, Shashi Bhushan; Shopov, Dimitar Y.; Sharninghausen, Liam S.
    • Journal of the American Chemical Society, Vol. 139, Issue 28
    • DOI: 10.1021/jacs.7b04874

    Revisiting the Redox Properties of Hydrous Iridium Oxide Films in the Context of Oxygen Evolution
    journal, September 2013

    • Steegstra, Patrick; Busch, Michael; Panas, Itai
    • The Journal of Physical Chemistry C, Vol. 117, Issue 40
    • DOI: 10.1021/jp407030r

    C−H Bond Activation of Thiophenes by Ir Complexes of the Hydrotris(3,5-dimethylpyrazolyl)borate Ligand, Tp Me2
    journal, January 1999

    • Paneque, Margarita; Poveda, Manuel L.; Salazar, Verónica
    • Organometallics, Vol. 18, Issue 2
    • DOI: 10.1021/om9804834

    Identification of an iridium-containing compound with a formal oxidation state of IX
    journal, October 2014

    • Wang, Guanjun; Zhou, Mingfei; Goettel, James T.
    • Nature, Vol. 514, Issue 7523
    • DOI: 10.1038/nature13795

    Closed-shell and open-shell square-planar iridium nitrido complexes
    journal, June 2012

    • Scheibel, Markus G.; Askevold, Bjorn; Heinemann, Frank W.
    • Nature Chemistry, Vol. 4, Issue 7
    • DOI: 10.1038/nchem.1368

    Metal L III -edge extended X-ray absorption fine structure of 5d transition-metal hexafluorides and related fluoroanions
    journal, January 1992

    • Brisdon, Alan K.; Holloway, John H.; Hope, Eric G.
    • Journal of the Chemical Society, Dalton Transactions, Issue 1
    • DOI: 10.1039/dt9920000139

    Hydroxyl Group-Prompted and Iridium(III)-Catalyzed Regioselective C−H Annulation of N -phenoxyacetamides with Propargyl Alcohols
    journal, May 2018

    • Chen, Weijie; Liu, Fu-Xiaomin; Gong, Wanchun
    • Advanced Synthesis & Catalysis, Vol. 360, Issue 13
    • DOI: 10.1002/adsc.201800322