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

Abstract

A complete series of Ir(iv) diastereomers coordinated with chlorides and bidentate pyridine-alkoxide ligands was prepared, revealing a number of significant unusual properties.

Authors:
 [1];  [2];  [3];  [4];  [2];  [2];  [2]
  1. Yale Univ., New Haven, CT (United States)
  2. Yale Univ., New Haven, CT (United States); Yale Univ., West Haven, CT (United States). Energy Sciences Inst.
  3. Yale Univ., New Haven, CT (United States); Consejo Superior de Investigaciones Cientificas (CSIC), Sevilla (Spain)
  4. Yale Univ., New Haven, CT (United States); Louisiana State Univ., Baton Rouge, LA (United States)
Publication Date:
Research Org.:
Energy Frontier Research Centers (EFRC) (United States). Argonne-Northwestern Solar Energy Research Center (ANSER); Northwestern Univ., Evanston, IL (United States)
Sponsoring Org.:
USDOE Office of Science (SC), Basic Energy Sciences (BES) (SC-22)
OSTI Identifier:
1388146
Grant/Contract Number:  
SC0001059
Resource Type:
Accepted Manuscript
Journal Name:
Chemical Science
Additional Journal Information:
Journal Volume: 8; Journal Issue: 2; Related Information: ANSER partners with Northwestern University (lead); Argonne National Laboratory; University of Chicago; University of Illinois, Urbana-Champaign; Yale University; Journal ID: ISSN 2041-6520
Publisher:
Royal Society of Chemistry
Country of Publication:
United States
Language:
English
Subject:
37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY

Citation Formats

Shopov, Dimitar Y., Rudshteyn, Benjamin, Campos, Jesús, Vinyard, David J., Batista, Victor S., Brudvig, Gary W., and Crabtree, Robert H. A full set of iridium( iv ) pyridine-alkoxide stereoisomers: highly geometry-dependent redox properties. United States: N. p., 2017. Web. doi:10.1039/c6sc03758e.
Shopov, Dimitar Y., Rudshteyn, Benjamin, Campos, Jesús, Vinyard, David J., Batista, Victor S., Brudvig, Gary W., & Crabtree, Robert H. A full set of iridium( iv ) pyridine-alkoxide stereoisomers: highly geometry-dependent redox properties. United States. doi:10.1039/c6sc03758e.
Shopov, Dimitar Y., Rudshteyn, Benjamin, Campos, Jesús, Vinyard, David J., Batista, Victor S., Brudvig, Gary W., and Crabtree, Robert H. Tue . "A full set of iridium( iv ) pyridine-alkoxide stereoisomers: highly geometry-dependent redox properties". United States. doi:10.1039/c6sc03758e. https://www.osti.gov/servlets/purl/1388146.
@article{osti_1388146,
title = {A full set of iridium( iv ) pyridine-alkoxide stereoisomers: highly geometry-dependent redox properties},
author = {Shopov, Dimitar Y. and Rudshteyn, Benjamin and Campos, Jesús and Vinyard, David J. and Batista, Victor S. and Brudvig, Gary W. and Crabtree, Robert H.},
abstractNote = {A complete series of Ir(iv) diastereomers coordinated with chlorides and bidentate pyridine-alkoxide ligands was prepared, revealing a number of significant unusual properties.},
doi = {10.1039/c6sc03758e},
journal = {Chemical Science},
number = 2,
volume = 8,
place = {United States},
year = {2017},
month = {11}
}

Journal Article:
Free Publicly Available Full Text
Publisher's Version of Record

Citation Metrics:
Cited by: 18 works
Citation information provided by
Web of Science

Figures / Tables:

Scheme 1 Scheme 1: Transformation of organometallic precursors to highly active water-oxidation catalysts. Proposed catalyst resting state shown on right, accounting for current structural uncertainty.

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Works referenced in this record:

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
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Precursor Transformation during Molecular Oxidation Catalysis with Organometallic Iridium Complexes
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  • Journal of the American Chemical Society, Vol. 135, Issue 29
  • DOI: 10.1021/ja4048762

Correlations between the ligand electrochemical parameter, EL(L), and the Hammett substituent parameter, .sigma.
journal, May 1993

  • Masui, Hitoshi; Lever, A. B. P.
  • Inorganic Chemistry, Vol. 32, Issue 10, p. 2199-2201
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Quinoxaline Excision:  A Novel Approach to Tri- and Diquinoxaline Cavitands
journal, February 2004

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Ultrafast and Ultraslow Oxygen Atom Transfer Reactions between Late Metal Centers
journal, January 2007

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  • Journal of the American Chemical Society, Vol. 129, Issue 3
  • DOI: 10.1021/ja065713h

The Slowest Water Exchange at a Homoleptic Mononuclear Metal Center:  Variable-Temperature and Variable-Pressure 17 O NMR Study on [Ir(H 2 O) 6 ] 3+
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Evaluation of Donor and Steric Properties of Anionic Ligands on High Valent Transition Metals
journal, December 2011

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Distinguishing Homogeneous from Heterogeneous Catalysis in Electrode-Driven Water Oxidation with Molecular Iridium Complexes
journal, July 2011

  • Schley, Nathan D.; Blakemore, James D.; Subbaiyan, Navaneetha K.
  • Journal of the American Chemical Society, Vol. 133, Issue 27
  • DOI: 10.1021/ja2004522

Computed Ligand Electronic Parameters from Quantum Chemistry and Their Relation to Tolman Parameters, Lever Parameters, and Hammett Constants
journal, November 2001

  • Perrin, Lionel; Clot, Eric; Eisenstein, Odile
  • Inorganic Chemistry, Vol. 40, Issue 23
  • DOI: 10.1021/ic0105258

Heterogenized Iridium Water-Oxidation Catalyst from a Silatrane Precursor
journal, July 2016

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  • ACS Catalysis, Vol. 6, Issue 8
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Activity and degradation pathways of pentamethyl-cyclopentadienyl-iridium catalysts for water oxidation
journal, January 2011

  • Savini, Arianna; Belanzoni, Paola; Bellachioma, Gianfranco
  • Green Chemistry, Vol. 13, Issue 12
  • DOI: 10.1039/c1gc15899f

Electrochemical Activation of Cp* Iridium Complexes for Electrode-Driven Water-Oxidation Catalysis
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  • DOI: 10.1021/ja5068299

Transformation of a Cp*-Iridium(III) Precatalyst for Water Oxidation when Exposed to Oxidative Stress
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Particle Formation during Oxidation Catalysis with Cp* Iridium Complexes
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Effective donor abilities of E-t-Bu and EPh (E = O, S, Se, Te) to a high valent transition metal
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Geometrical and optical benchmarking of copper guanidine-quinoline complexes: Insights from TD-DFT and many-body perturbation theory
journal, October 2013

  • Jesser, Anton; Rohrmüller, Martin; Schmidt, Wolf Gero
  • Journal of Computational Chemistry, Vol. 35, Issue 1
  • DOI: 10.1002/jcc.23449

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

Isolated Ir(V) Boryl Complexes and Their Reactions with Hydrocarbons
journal, August 2001

  • Kawamura, Kazumori; Hartwig, John F.
  • Journal of the American Chemical Society, Vol. 123, Issue 34
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An NMR Study of the Oxidative Degradation of Cp*Ir Catalysts for Water Oxidation: Evidence for a Preliminary Attack on the Quaternary Carbon Atom of the ­-C-CH3 Moiety
journal, November 2011

  • Zuccaccia, Cristiano; Bellachioma, Gianfranco; Bolaño, Sandra
  • European Journal of Inorganic Chemistry, Vol. 2012, Issue 9
  • DOI: 10.1002/ejic.201100954

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
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gem -Disubstituent Effect:  Theoretical Basis and Synthetic Applications
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journal, March 2015

  • Sheehan, Stafford W.; Thomsen, Julianne M.; Hintermair, Ulrich
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  • DOI: 10.1038/ncomms7469

Stoichiometric Oxy Functionalization and CH Activation Studies of Cyclometalated Iridium(III) 6-Phenyl-2,2‘-Bipyridine Hydrocarbyl Complexes
journal, April 2007

  • Young, Kenneth J. H.; Mironov, Oleg A.; Periana, Roy A.
  • Organometallics, Vol. 26, Issue 9
  • DOI: 10.1021/om0611002

Chemical Redox Agents for Organometallic Chemistry
journal, January 1996

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New Ir Bis-Carbonyl Precursor for Water Oxidation Catalysis
journal, February 2016


Substitution inertness of [Ir(H2O)6]3+
journal, January 1987


Synthesis and Characterization of Facial and Meridional Tris-cyclometalated Iridium(III) Complexes
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    Works referencing / citing this record:

    CCDC 1497501: Experimental Crystal Structure Determination: IBAHEB : trans-Cl,trans-O,trans-N-bis(2-(pyridin-2-yl)propan-2-olato)-dichloro-iridium(iv)
    dataset, August 2016


    CCDC 1497502: Experimental Crystal Structure Determination: IBAHIF : trans-Cl,cis-O,cis-N-bis(2-(pyridin-2-yl)propan-2-olato)-dichloro-iridium(iv)
    dataset, August 2016


    CCDC 1497507: Experimental Crystal Structure Determination: IBAJAZ : Sodium (2-(pyridin-2-yl)propan-2-olato)-tetrachloro-iridium(iv)
    dataset, August 2016


    Synthesis and Characterization of Iridium(V) Coordination Complexes With an N,O-Donor Organic Ligand
    journal, September 2017

    • Sharninghausen, Liam S.; Sinha, Shashi Bhushan; Shopov, Dimitar Y.
    • Angewandte Chemie International Edition, Vol. 56, Issue 42
    • DOI: 10.1002/anie.201707593

    Metalloradicals Supported by a meta -Carborane Ligand
    journal, May 2019

    • Cui, Peng-Fei; Gao, Yang; Guo, Shu-Ting
    • Angewandte Chemie International Edition, Vol. 58, Issue 24
    • DOI: 10.1002/anie.201903467

    Transformation of a Cp*-Iridium(III) Precatalyst for Water Oxidation when Exposed to Oxidative Stress
    journal, February 2014

    • Zuccaccia, Cristiano; Bellachioma, Gianfranco; Bortolini, Olga
    • Chemistry - A European Journal, Vol. 20, Issue 12
    • DOI: 10.1002/chem.201304412

    An NMR Study of the Oxidative Degradation of Cp*Ir Catalysts for Water Oxidation: Evidence for a Preliminary Attack on the Quaternary Carbon Atom of the ­-C-CH3 Moiety
    journal, November 2011

    • Zuccaccia, Cristiano; Bellachioma, Gianfranco; Bolaño, Sandra
    • European Journal of Inorganic Chemistry, Vol. 2012, Issue 9
    • DOI: 10.1002/ejic.201100954

    Geometrical and optical benchmarking of copper guanidine-quinoline complexes: Insights from TD-DFT and many-body perturbation theory
    journal, October 2013

    • Jesser, Anton; Rohrmüller, Martin; Schmidt, Wolf Gero
    • Journal of Computational Chemistry, Vol. 35, Issue 1
    • DOI: 10.1002/jcc.23449

    New Ir Bis-Carbonyl Precursor for Water Oxidation Catalysis
    journal, February 2016


    Heterogenized Iridium Water-Oxidation Catalyst from a Silatrane Precursor
    journal, July 2016

    • Materna, Kelly L.; Rudshteyn, Benjamin; Brennan, Bradley J.
    • ACS Catalysis, Vol. 6, Issue 8
    • DOI: 10.1021/acscatal.6b01101

    Chemical Redox Agents for Organometallic Chemistry
    journal, January 1996

    • Connelly, Neil G.; Geiger, William E.
    • Chemical Reviews, Vol. 96, Issue 2
    • DOI: 10.1021/cr940053x

    gem -Disubstituent Effect:  Theoretical Basis and Synthetic Applications
    journal, May 2005

    • Jung, Michael E.; Piizzi, Grazia
    • Chemical Reviews, Vol. 105, Issue 5
    • DOI: 10.1021/cr940337h

    Correlations between the ligand electrochemical parameter, EL(L), and the Hammett substituent parameter, .sigma.
    journal, May 1993

    • Masui, Hitoshi; Lever, A. B. P.
    • Inorganic Chemistry, Vol. 32, Issue 10, p. 2199-2201
    • DOI: 10.1021/ic00062a052

    Computed Ligand Electronic Parameters from Quantum Chemistry and Their Relation to Tolman Parameters, Lever Parameters, and Hammett Constants
    journal, November 2001

    • Perrin, Lionel; Clot, Eric; Eisenstein, Odile
    • Inorganic Chemistry, Vol. 40, Issue 23
    • DOI: 10.1021/ic0105258

    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

    Isolated Ir(V) Boryl Complexes and Their Reactions with Hydrocarbons
    journal, August 2001

    • Kawamura, Kazumori; Hartwig, John F.
    • Journal of the American Chemical Society, Vol. 123, Issue 34
    • DOI: 10.1021/ja015975d

    Synthesis and Characterization of Facial and Meridional Tris-cyclometalated Iridium(III) Complexes
    journal, June 2003

    • Tamayo, Arnold B.; Alleyne, Bert D.; Djurovich, Peter I.
    • Journal of the American Chemical Society, Vol. 125, Issue 24
    • DOI: 10.1021/ja034537z

    Ultrafast and Ultraslow Oxygen Atom Transfer Reactions between Late Metal Centers
    journal, January 2007

    • Fortner, Kevin C.; Laitar, David S.; Muldoon, John
    • Journal of the American Chemical Society, Vol. 129, Issue 3
    • DOI: 10.1021/ja065713h

    Distinguishing Homogeneous from Heterogeneous Catalysis in Electrode-Driven Water Oxidation with Molecular Iridium Complexes
    journal, July 2011

    • Schley, Nathan D.; Blakemore, James D.; Subbaiyan, Navaneetha K.
    • Journal of the American Chemical Society, Vol. 133, Issue 27
    • DOI: 10.1021/ja2004522

    Particle Formation during Oxidation Catalysis with Cp* Iridium Complexes
    journal, May 2012

    • Hintermair, Ulrich; Hashmi, Sara M.; Elimelech, Menachem
    • Journal of the American Chemical Society, Vol. 134, Issue 23
    • DOI: 10.1021/ja3033026

    Precursor Transformation during Molecular Oxidation Catalysis with Organometallic Iridium Complexes
    journal, July 2013

    • Hintermair, Ulrich; Sheehan, Stafford W.; Parent, Alexander R.
    • Journal of the American Chemical Society, Vol. 135, Issue 29
    • DOI: 10.1021/ja4048762

    Electrochemical Activation of Cp* Iridium Complexes for Electrode-Driven Water-Oxidation Catalysis
    journal, September 2014

    • Thomsen, Julianne M.; Sheehan, Stafford W.; Hashmi, Sara M.
    • Journal of the American Chemical Society, Vol. 136, Issue 39
    • DOI: 10.1021/ja5068299

    The Slowest Water Exchange at a Homoleptic Mononuclear Metal Center:  Variable-Temperature and Variable-Pressure 17 O NMR Study on [Ir(H 2 O) 6 ] 3+
    journal, January 1996

    • Cusanelli, Antonio; Frey, Urban; Richens, David T.
    • Journal of the American Chemical Society, Vol. 118, Issue 22
    • DOI: 10.1021/ja954071n

    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

    Quinoxaline Excision:  A Novel Approach to Tri- and Diquinoxaline Cavitands
    journal, February 2004

    • Castro, Peter P.; Zhao, Gang; Masangkay, Grace A.
    • Organic Letters, Vol. 6, Issue 3
    • DOI: 10.1021/ol036045x

    Stoichiometric Oxy Functionalization and CH Activation Studies of Cyclometalated Iridium(III) 6-Phenyl-2,2‘-Bipyridine Hydrocarbyl Complexes
    journal, April 2007

    • Young, Kenneth J. H.; Mironov, Oleg A.; Periana, Roy A.
    • Organometallics, Vol. 26, Issue 9
    • DOI: 10.1021/om0611002

    A molecular catalyst for water oxidation that binds to metal oxide surfaces
    journal, March 2015

    • Sheehan, Stafford W.; Thomsen, Julianne M.; Hintermair, Ulrich
    • Nature Communications, Vol. 6, Issue 1
    • DOI: 10.1038/ncomms7469

    Activity and degradation pathways of pentamethyl-cyclopentadienyl-iridium catalysts for water oxidation
    journal, January 2011

    • Savini, Arianna; Belanzoni, Paola; Bellachioma, Gianfranco
    • Green Chemistry, Vol. 13, Issue 12
    • DOI: 10.1039/c1gc15899f

    Stable iridium( iv ) complexes supported by tetradentate salen ligands. Synthesis, structures and reactivity
    journal, January 2019

    • Lee, Chi Lun; Wu, Liangliang; Huang, Jie-Sheng
    • Chemical Communications, Vol. 55, Issue 25
    • DOI: 10.1039/c8cc10220a

    Synthesis and Characterization of Iridium(V) Coordination Complexes With an N,O-Donor Organic Ligand
    journal, September 2017

    • Sharninghausen, Liam S.; Sinha, Shashi Bhushan; Shopov, Dimitar Y.
    • Angewandte Chemie International Edition, Vol. 56, Issue 42
    • DOI: 10.1002/anie.201707593

    Metalloradicals Supported by a meta -Carborane Ligand
    journal, May 2019

    • Cui, Peng-Fei; Gao, Yang; Guo, Shu-Ting
    • Angewandte Chemie International Edition, Vol. 58, Issue 24
    • DOI: 10.1002/anie.201903467

    Stable iridium( iv ) complexes supported by tetradentate salen ligands. Synthesis, structures and reactivity
    journal, January 2019

    • Lee, Chi Lun; Wu, Liangliang; Huang, Jie-Sheng
    • Chemical Communications, Vol. 55, Issue 25
    • DOI: 10.1039/c8cc10220a