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Title: Mechanistic basis for tuning iridium hydride photochemistry from H 2 evolution to hydride transfer hydrodechlorination

Abstract

The innate H 2 evolution photochemistry of an iridium hydride complex is diverted towards photochemical hydrodechlorination of dichloromethane with high selectivity and quantum yield.

Authors:
ORCiD logo [1];  [2]; ORCiD logo [1]; ORCiD logo [2]; ORCiD logo [2]; ORCiD logo [2]; ORCiD logo [2]
  1. Department of Chemistry, University of North Carolina at Chapel Hill, Chapel Hill, USA, Department of Chemistry
  2. Department of Chemistry, University of North Carolina at Chapel Hill, Chapel Hill, USA
Publication Date:
Sponsoring Org.:
USDOE Office of Science (SC), Basic Energy Sciences (BES) (SC-22)
OSTI Identifier:
1605045
Grant/Contract Number:  
SC0001011; SC0014255
Resource Type:
Published Article
Journal Name:
Chemical Science
Additional Journal Information:
Journal Name: Chemical Science; Journal ID: ISSN 2041-6520
Publisher:
Royal Society of Chemistry (RSC)
Country of Publication:
United Kingdom
Language:
English

Citation Formats

Barrett, Seth M., Stratakes, Bethany M., Chambers, Matthew B., Kurtz, Daniel A., Pitman, Catherine L., Dempsey, Jillian L., and Miller, Alexander J. M. Mechanistic basis for tuning iridium hydride photochemistry from H 2 evolution to hydride transfer hydrodechlorination. United Kingdom: N. p., 2020. Web. doi:10.1039/D0SC00422G.
Barrett, Seth M., Stratakes, Bethany M., Chambers, Matthew B., Kurtz, Daniel A., Pitman, Catherine L., Dempsey, Jillian L., & Miller, Alexander J. M. Mechanistic basis for tuning iridium hydride photochemistry from H 2 evolution to hydride transfer hydrodechlorination. United Kingdom. doi:10.1039/D0SC00422G.
Barrett, Seth M., Stratakes, Bethany M., Chambers, Matthew B., Kurtz, Daniel A., Pitman, Catherine L., Dempsey, Jillian L., and Miller, Alexander J. M. Wed . "Mechanistic basis for tuning iridium hydride photochemistry from H 2 evolution to hydride transfer hydrodechlorination". United Kingdom. doi:10.1039/D0SC00422G.
@article{osti_1605045,
title = {Mechanistic basis for tuning iridium hydride photochemistry from H 2 evolution to hydride transfer hydrodechlorination},
author = {Barrett, Seth M. and Stratakes, Bethany M. and Chambers, Matthew B. and Kurtz, Daniel A. and Pitman, Catherine L. and Dempsey, Jillian L. and Miller, Alexander J. M.},
abstractNote = {The innate H 2 evolution photochemistry of an iridium hydride complex is diverted towards photochemical hydrodechlorination of dichloromethane with high selectivity and quantum yield.},
doi = {10.1039/D0SC00422G},
journal = {Chemical Science},
number = ,
volume = ,
place = {United Kingdom},
year = {2020},
month = {1}
}

Journal Article:
Free Publicly Available Full Text
Publisher's Version of Record
DOI: 10.1039/D0SC00422G

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Works referenced in this record:

Photochemical carbonylation of benzene by iridium(I) and rhodium(I) square-planar complexes
journal, February 1986

  • Kunin, Amanda J.; Eisenberg, Richard.
  • Journal of the American Chemical Society, Vol. 108, Issue 3
  • DOI: 10.1021/ja00263a045

Photosensitized, energy transfer-mediated organometallic catalysis through electronically excited nickel(II)
journal, January 2017


Organotin hydrides and organic free radicals
journal, October 1968


Organic Photoredox Catalysis
journal, June 2016


Photochemistry of metal carbonyls
journal, August 1974


Efficient Photochemical Dihydrogen Generation Initiated by a Bimetallic Self-Quenching Mechanism
journal, October 2016

  • Chambers, Matthew B.; Kurtz, Daniel A.; Pitman, Catherine L.
  • Journal of the American Chemical Society, Vol. 138, Issue 41
  • DOI: 10.1021/jacs.6b08701

Photochemical dehydrogenation of alkanes catalyzed by trans-carbonylchlorobis(trimethylphosphine)rhodium: aspects of selectivity and mechanism
journal, August 1989

  • Maguire, John A.; Boese, William T.; Goldman, Alan S.
  • Journal of the American Chemical Society, Vol. 111, Issue 18
  • DOI: 10.1021/ja00200a030

Photooxidation of Platinum(II) Diimine Dithiolates
journal, December 1997

  • Connick, William B.; Gray, Harry B.
  • Journal of the American Chemical Society, Vol. 119, Issue 48
  • DOI: 10.1021/ja9723803

Molecular Photosensitizers in Energy Research and Catalysis: Design Principles and Recent Developments
journal, January 2019


The Tandem Photoredox Catalysis Mechanism of [Ir(ppy) 2 (dtb-bpy)] + Enabling Access to Energy Demanding Organic Substrates
journal, September 2019

  • Connell, Timothy U.; Fraser, Catherine L.; Czyz, Milena L.
  • Journal of the American Chemical Society, Vol. 141, Issue 44
  • DOI: 10.1021/jacs.9b07370

Visible Light Photoredox Catalysis with Transition Metal Complexes: Applications in Organic Synthesis
journal, March 2013

  • Prier, Christopher K.; Rankic, Danica A.; MacMillan, David W. C.
  • Chemical Reviews, Vol. 113, Issue 7
  • DOI: 10.1021/cr300503r

The merger of transition metal and photocatalysis
journal, July 2017


Dye-Sensitized Solar Cells
journal, November 2010

  • Hagfeldt, Anders; Boschloo, Gerrit; Sun, Licheng
  • Chemical Reviews, Vol. 110, Issue 11
  • DOI: 10.1021/cr900356p

Stereoselectivity and kinetic control of hydrogen oxidative addition to iridium(I) complexes
journal, December 1983

  • Johnson, Curtis E.; Fisher, Barbara J.; Eisenberg, Richard
  • Journal of the American Chemical Society, Vol. 105, Issue 26
  • DOI: 10.1021/ja00364a066

Mechanism of Reduction of Alkyl Halides by Organotin Hydrides
journal, August 1964

  • Menapace, Lawrence W.; Kuivila, Henry G.
  • Journal of the American Chemical Society, Vol. 86, Issue 15
  • DOI: 10.1021/ja01069a015

Photochemistry of Transition Metal Hydrides
journal, June 2016


Photochemistry of tris(2,2'-bipyridine)ruthenium(2+) ion (Ru(bpy)32+). Solvent effects
journal, August 1983

  • Caspar, Jonathan V.; Meyer, Thomas J.
  • Journal of the American Chemical Society, Vol. 105, Issue 17
  • DOI: 10.1021/ja00355a009

Molecular Photoelectrocatalysts for Visible Light-Driven Hydrogen Evolution from Neutral Water
journal, July 2014

  • Pitman, Catherine L.; Miller, Alexander J. M.
  • ACS Catalysis, Vol. 4, Issue 8
  • DOI: 10.1021/cs500441f

Decarboxylative sp3 C–N coupling via dual copper and photoredox catalysis
journal, June 2018


Excited-State Switching between Ligand-Centered and Charge Transfer Modulated by Metal–Carbon Bonds in Cyclopentadienyl Iridium Complexes
journal, December 2018


Long-Lived Charge-Transfer States of Nickel(II) Aryl Halide Complexes Facilitate Bimolecular Photoinduced Electron Transfer
journal, February 2018

  • Shields, Benjamin J.; Kudisch, Bryan; Scholes, Gregory D.
  • Journal of the American Chemical Society, Vol. 140, Issue 8
  • DOI: 10.1021/jacs.7b13281

Spectroscopic behavior of a new family of mixed-ligand iridium(III) complexes
journal, September 1989


Hydrogen Production by Molecular Photocatalysis
journal, October 2007

  • Esswein, Arthur J.; Nocera, Daniel G.
  • Chemical Reviews, Vol. 107, Issue 10
  • DOI: 10.1021/cr050193e

Characterizing chain processes in visible light photoredox catalysis
journal, January 2015

  • Cismesia, Megan A.; Yoon, Tehshik P.
  • Chemical Science, Vol. 6, Issue 10
  • DOI: 10.1039/C5SC02185E

Controlling Emission Energy, Self-Quenching, and Excimer Formation in Highly Luminescent N∧C∧N-Coordinated Platinum(II) Complexes
journal, December 2005

  • Farley, Sarah J.; Rochester, David L.; Thompson, Amber L.
  • Inorganic Chemistry, Vol. 44, Issue 26
  • DOI: 10.1021/ic051049e

Illuminating Photoredox Catalysis
journal, April 2019


Photoinduced Ullmann C-N Coupling: Demonstrating the Viability of a Radical Pathway
journal, November 2012


Photochemical Production of Ethane from an Iridium Methyl Complex
journal, May 2017


Photoswitchable Hydride Transfer from Iridium to 1-Methylnicotinamide Rationalized by Thermochemical Cycles
journal, October 2014

  • Barrett, Seth M.; Pitman, Catherine L.; Walden, Andrew G.
  • Journal of the American Chemical Society, Vol. 136, Issue 42
  • DOI: 10.1021/ja508762g

Electron-Transfer Photoredox Catalysis: Development of a Tin-Free Reductive Dehalogenation Reaction
journal, July 2009

  • Narayanam, Jagan M. R.; Tucker, Joseph W.; Stephenson, Corey R. J.
  • Journal of the American Chemical Society, Vol. 131, Issue 25
  • DOI: 10.1021/ja9033582

Photoexcitation of flavoenzymes enables a stereoselective radical cyclization
journal, June 2019


Metal centered ligand field excited states: Their roles in the design and performance of transition metal based photochemical molecular devices
journal, March 2011


Highly Solvent Dependent Luminescence from [Ru(bpy) n (dppp2) 3− n ] 2+ ( n = 0−2)
journal, June 2010

  • Sun, Yujie; Turro, Claudia
  • Inorganic Chemistry, Vol. 49, Issue 11
  • DOI: 10.1021/ic100106b

Copper-Catalyzed Alkylation of Aliphatic Amines Induced by Visible Light
journal, November 2017

  • Matier, Carson D.; Schwaben, Jonas; Peters, Jonas C.
  • Journal of the American Chemical Society, Vol. 139, Issue 49
  • DOI: 10.1021/jacs.7b09582

Excited-State Self-Quenching Reactions of Square Planar Platinum(II) Diimine Complexes in Room-Temperature Fluid Solution
journal, July 1999

  • Connick, William B.; Geiger, David; Eisenberg, Richard
  • Inorganic Chemistry, Vol. 38, Issue 14
  • DOI: 10.1021/ic981387y

Photochemical Formic Acid Dehydrogenation by Iridium Complexes: Understanding Mechanism and Overcoming Deactivation
journal, September 2015

  • Barrett, Seth M.; Slattery, Samuel A.; Miller, Alexander J. M.
  • ACS Catalysis, Vol. 5, Issue 11
  • DOI: 10.1021/acscatal.5b01995

Molecular Chemistry of Consequence to Renewable Energy
journal, October 2005

  • Dempsey, Jillian L.; Esswein, Arthur J.; Manke, David R.
  • Inorganic Chemistry, Vol. 44, Issue 20
  • DOI: 10.1021/ic0509276

Photoinduced, Copper-Catalyzed Alkylation of Amides with Unactivated Secondary Alkyl Halides at Room Temperature
journal, January 2014

  • Do, Hien-Quang; Bachman, Shoshana; Bissember, Alex C.
  • Journal of the American Chemical Society, Vol. 136, Issue 5
  • DOI: 10.1021/ja4126609

MLCT excited states of cuprous bis-phenanthroline coordination compounds
journal, October 2000

  • Scaltrito, Donald V.; Thompson, David W.; O'Callaghan, John A.
  • Coordination Chemistry Reviews, Vol. 208, Issue 1
  • DOI: 10.1016/S0010-8545(00)00309-X

Excited-State Deprotonation and H/D Exchange of an Iridium Hydride Complex
journal, November 2003

  • Suenobu, Tomoyoshi; Guldi, Dirk M.; Ogo, Seiji
  • Angewandte Chemie International Edition, Vol. 42, Issue 44
  • DOI: 10.1002/anie.200352061

Direct C–C Bond Formation from Alkanes Using Ni-Photoredox Catalysis
journal, October 2018

  • Ackerman, Laura K. G.; Martinez Alvarado, Jesus I.; Doyle, Abigail G.
  • Journal of the American Chemical Society, Vol. 140, Issue 43
  • DOI: 10.1021/jacs.8b09191

Ru(II) polypyridine complexes: photophysics, photochemistry, eletrochemistry, and chemiluminescence
journal, March 1988


Asymmetric copper-catalyzed C-N cross-couplings induced by visible light
journal, February 2016


Molecular Photoelectrocatalysts for Light-Driven Hydrogen Production
journal, April 2018


Electronic structure of catalytic intermediates for production of H2: (C5Me5)Ir(bpy) and its conjugated acid
journal, October 1992


Photophysics, photochemistry and solar energy conversion with tris(bipyridyl)ruthenium(II) and its analogues
journal, October 1982


Photochemistry of tris(2,2'-bipyridine)ruthenium(2+) ion
journal, September 1982

  • Durham, Bill; Caspar, Jonathan V.; Nagle, Jeffrey K.
  • Journal of the American Chemical Society, Vol. 104, Issue 18
  • DOI: 10.1021/ja00382a012

Photochemical production of hydrogen and carbon dioxide from formate using mixed-ligand iridium complexes as catalysts
journal, July 1992


Chemistry of Personalized Solar Energy
journal, November 2009


Catalytic Disproportionation of Formic Acid to Generate Methanol
journal, February 2013

  • Miller, Alexander J. M.; Heinekey, D. Michael; Mayer, James M.
  • Angewandte Chemie International Edition, Vol. 52, Issue 14
  • DOI: 10.1002/anie.201208470

The photophysics of photoredox catalysis: a roadmap for catalyst design
journal, January 2016

  • Arias-Rotondo, Daniela M.; McCusker, James K.
  • Chemical Society Reviews, Vol. 45, Issue 21
  • DOI: 10.1039/C6CS00526H

Photoinduced Copper-Catalyzed Coupling of Terminal Alkynes and Alkyl Iodides
journal, April 2018

  • Hazra, Avijit; Lee, Mitchell T.; Chiu, Justin F.
  • Angewandte Chemie International Edition, Vol. 57, Issue 19
  • DOI: 10.1002/anie.201801085

Study of the Mechanism of Photochemical Carbonylation of Benzene Catalyzed by Rh(PMe3)2(CO)Cl
journal, October 1994

  • Rosini, Glen P.; Boese, William T.; Goldman, Alan S.
  • Journal of the American Chemical Society, Vol. 116, Issue 21
  • DOI: 10.1021/ja00100a013

Metal-Mediated Reductive Hydrodehalogenation of Organic Halides
journal, November 2002

  • Alonso, Francisco; Beletskaya, Irina P.; Yus, Miguel
  • Chemical Reviews, Vol. 102, Issue 11
  • DOI: 10.1021/cr0102967

Photocatalysis of the Homogeneous Water-Gas Shift Reaction under Ambient Conditions by Cationic Iridium(III) Complexes
journal, July 1991

  • Ziessel, Raymond
  • Angewandte Chemie International Edition in English, Vol. 30, Issue 7
  • DOI: 10.1002/anie.199108441

Visible light photoredox catalysis: applications in organic synthesis
journal, January 2011

  • Narayanam, Jagan M. R.; Stephenson, Corey R. J.
  • Chem. Soc. Rev., Vol. 40, Issue 1
  • DOI: 10.1039/B913880N