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Title: Concerted proton-electron transfer oxidation of phenols and hydrocarbons by a high-valent nickel complex

Abstract

A high-valent nickel(III) compound performs fast concerted proton–electron transfer on O–H and C–H bonds. Thermodynamic analysis suggests that the oxidizing power of the compound and the formation of a strong ligand O–H bond lead to high reactivity.

Authors:
 [1];  [1];  [1];  [1]; ORCiD logo [1]; ORCiD logo [1]
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  1. Department of Chemistry, Yale University, New Haven, USA
Publication Date:
Sponsoring Org.:
USDOE Office of Science (SC), Basic Energy Sciences (BES) (SC-22)
OSTI Identifier:
1582476
Grant/Contract Number:  
SC0001059
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

Fisher, Katherine J., Feuer, Margalit L., Lant, Hannah M. C., Mercado, Brandon Q., Crabtree, Robert H., and Brudvig, Gary W. Concerted proton-electron transfer oxidation of phenols and hydrocarbons by a high-valent nickel complex. United Kingdom: N. p., 2020. Web. doi:10.1039/C9SC05565G.
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Fisher, Katherine J., Feuer, Margalit L., Lant, Hannah M. C., Mercado, Brandon Q., Crabtree, Robert H., & Brudvig, Gary W. Concerted proton-electron transfer oxidation of phenols and hydrocarbons by a high-valent nickel complex. United Kingdom. doi:10.1039/C9SC05565G.
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Fisher, Katherine J., Feuer, Margalit L., Lant, Hannah M. C., Mercado, Brandon Q., Crabtree, Robert H., and Brudvig, Gary W. Wed . "Concerted proton-electron transfer oxidation of phenols and hydrocarbons by a high-valent nickel complex". United Kingdom. doi:10.1039/C9SC05565G.
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@article{osti_1582476,
title = {Concerted proton-electron transfer oxidation of phenols and hydrocarbons by a high-valent nickel complex},
author = {Fisher, Katherine J. and Feuer, Margalit L. and Lant, Hannah M. C. and Mercado, Brandon Q. and Crabtree, Robert H. and Brudvig, Gary W.},
abstractNote = {A high-valent nickel(III) compound performs fast concerted proton–electron transfer on O–H and C–H bonds. Thermodynamic analysis suggests that the oxidizing power of the compound and the formation of a strong ligand O–H bond lead to high reactivity.},
doi = {10.1039/C9SC05565G},
journal = {Chemical Science},
number = ,
volume = ,
place = {United Kingdom},
year = {2020},
month = {1}
}
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DOI: 10.1039/C9SC05565G
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Works referenced in this record:

Mn-, Fe-, and Co-Catalyzed Radical Hydrofunctionalizations of Olefins
journal, June 2016

Nickel Superoxide Dismutase Structure and Mechanism †
journal, June 2004

  • Barondeau, David P.; Kassmann, Carey J.; Bruns, Cami K.
  • Biochemistry, Vol. 43, Issue 25
  • DOI: 10.1021/bi0496081

Tuning the Reactivity of Terminal Nickel(III)–Oxygen Adducts for C–H Bond Activation
journal, October 2016

  • Pirovano, Paolo; Farquhar, Erik R.; Swart, Marcel
  • Journal of the American Chemical Society, Vol. 138, Issue 43
  • DOI: 10.1021/jacs.6b08406

Chemistry of the t -Butoxyl Radical:  Evidence that Most Hydrogen Abstractions from Carbon are Entropy-Controlled
journal, June 2004

  • Finn, Meghan; Friedline, Robert; Suleman, N. Kamrudin
  • Journal of the American Chemical Society, Vol. 126, Issue 24
  • DOI: 10.1021/ja0493493

Oxygen-hydrogen bond dissociation energies in para-substituted phenols
journal, June 1988

  • Mulder, P.; Saastad, O. W.; Griller, D.
  • Journal of the American Chemical Society, Vol. 110, Issue 12
  • DOI: 10.1021/ja00220a088

Proton-Coupled Electron Transfer in Organic Synthesis: Fundamentals, Applications, and Opportunities
journal, May 2016

  • Miller, David C.; Tarantino, Kyle T.; Knowles, Robert R.
  • Topics in Current Chemistry, Vol. 374, Issue 3
  • DOI: 10.1007/s41061-016-0030-6

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

Thermochemistry of Proton-Coupled Electron Transfer Reagents and its Implications
journal, December 2010

  • Warren, Jeffrey J.; Tronic, Tristan A.; Mayer, James M.
  • Chemical Reviews, Vol. 110, Issue 12
  • DOI: 10.1021/cr100085k

C−H Bond Activation by a Ferric Methoxide Complex:  Modeling the Rate-Determining Step in the Mechanism of Lipoxygenase
journal, January 2002

  • Goldsmith, Christian R.; Jonas, Robert T.; Stack, T. Daniel P.
  • Journal of the American Chemical Society, Vol. 124, Issue 1
  • DOI: 10.1021/ja016451g

Electrocatalytic water oxidation by a molecular cobalt complex through a high valent cobalt oxo intermediate
journal, January 2016

  • Das, Debasree; Pattanayak, Santanu; Singh, Kundan K.
  • Chemical Communications, Vol. 52, Issue 79
  • DOI: 10.1039/C6CC05773J

A Pyridine Alkoxide Chelate Ligand That Promotes Both Unusually High Oxidation States and Water-Oxidation Catalysis
journal, February 2017

  • Michaelos, Thoe K.; Shopov, Dimitar Y.; Sinha, Shashi Bhushan
  • Accounts of Chemical Research, Vol. 50, Issue 4
  • DOI: 10.1021/acs.accounts.6b00652

Mechanistic Implications of Proton Transfer Coupled to Electron Transfer
journal, October 2001

  • Lebeau, Estelle L.; Binstead, Robert A.; Meyer, Thomas J.
  • Journal of the American Chemical Society, Vol. 123, Issue 43
  • DOI: 10.1021/ja000517a

Monomeric Mn III/II and Fe III/II Complexes with Terminal Hydroxo and Oxo Ligands:  Probing Reactivity via O−H Bond Dissociation Energies
journal, October 2003

  • Gupta, Rajeev; Borovik, A. S.
  • Journal of the American Chemical Society, Vol. 125, Issue 43
  • DOI: 10.1021/ja030149l

pKa values in organic chemistry – Making maximum use of the available data
journal, October 2018

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

Mechanism of phenol oxidation by heterodinuclear Ni Cu bis(μ-oxo) complexes involving nucleophilic oxo groups
journal, January 2014

  • Kundu, Subrata; Miceli, Enrico; Farquhar, Erik R.
  • Dalton Trans., Vol. 43, Issue 11
  • DOI: 10.1039/C3DT52644E

A Dinuclear Iridium(V,V) Oxo-Bridged Complex Characterized Using a Bulk Electrolysis Technique for Crystallizing Highly Oxidizing Compounds
journal, April 2018

Bond Strengths of Toluenes, Anilines, and Phenols:  To Hammett or Not
journal, May 2004

  • Pratt, Derek A.; DiLabio, Gino A.; Mulder, Peter
  • Accounts of Chemical Research, Vol. 37, Issue 5
  • DOI: 10.1021/ar010010k

Proton-Coupled Electron Transfer
journal, April 2012

  • Weinberg, David R.; Gagliardi, Christopher J.; Hull, Jonathan F.
  • Chemical Reviews, Vol. 112, Issue 7
  • DOI: 10.1021/cr200177j

Enthalpy of Formation of the Cyclohexadienyl Radical and the C−H Bond Enthalpy of 1,4-Cyclohexadiene: An Experimental and Computational Re-Evaluation
journal, June 2009

  • Gao, Yide; DeYonker, Nathan J.; Garrett, E. Chauncey
  • The Journal of Physical Chemistry A, Vol. 113, Issue 25
  • DOI: 10.1021/jp901314y

The first crystal structure of a monomeric phenoxyl radical: 2,4,6-tri-tert-butylphenoxyl radical
journal, January 2008

  • Manner, Virginia W.; Markle, Todd F.; Freudenthal, John H.
  • Chem. Commun., Issue 2
  • DOI: 10.1039/B712872J

Mechanism of Oxidation Reactions Catalyzed by Cytochrome P450 Enzymes
journal, September 2004

  • Meunier, Bernard; de Visser, Samuël P.; Shaik, Sason
  • Chemical Reviews, Vol. 104, Issue 9
  • DOI: 10.1021/cr020443g

Insight into the Structure and Mechanism of Nickel-Containing Superoxide Dismutase Derived from Peptide-Based Mimics
journal, May 2014

  • Shearer, Jason
  • Accounts of Chemical Research, Vol. 47, Issue 8
  • DOI: 10.1021/ar500060s

Hydrogen Atom Transfer by a High-Valent Nickel-Chloride Complex
journal, January 2018

  • Mondal, Prasenjit; Pirovano, Paolo; Das, Ankita
  • Journal of the American Chemical Society, Vol. 140, Issue 5
  • DOI: 10.1021/jacs.7b11953

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, Vol. 129, Issue 42
  • DOI: 10.1002/ange.201707593

Characterization and Reactivity of a Terminal Nickel(III)-Oxygen Adduct
journal, January 2015

  • Pirovano, Paolo; Farquhar, Erik R.; Swart, Marcel
  • Chemistry - A European Journal, Vol. 21, Issue 9
  • DOI: 10.1002/chem.201406485

C−H Bond Cleavage with Reductants: Re-Investigating the Reactivity of Monomeric Mn III/IV −Oxo Complexes and the Role of Oxo Ligand Basicity
journal, March 2009

  • Parsell, Trenton H.; Yang, Meng-Yin; Borovik, A. S.
  • Journal of the American Chemical Society, Vol. 131, Issue 8
  • DOI: 10.1021/ja8100825

Probing the Compound I-like Reactivity of a Bare High-Valent Oxo Iron Porphyrin Complex:  The Oxidation of Tertiary Amines
journal, March 2008

  • Chiavarino, Barbara; Cipollini, Romano; Crestoni, Maria Elisa
  • Journal of the American Chemical Society, Vol. 130, Issue 10
  • DOI: 10.1021/ja077286t

Oxidizing species in the mechanism of cytochrome P450
journal, May 2002

  • Ortiz de Montellano, Paul R.; De Voss, James J.
  • Natural Product Reports, Vol. 19, Issue 4
  • DOI: 10.1039/b101297p

Water-Nucleophilic Attack Mechanism for the Cu II (pyalk) 2 Water-Oxidation Catalyst
journal, July 2018

  • Rudshteyn, Benjamin; Fisher, Katherine J.; Lant, Hannah M. C.
  • ACS Catalysis, Vol. 8, Issue 9
  • DOI: 10.1021/acscatal.8b02466

A general treatment of hydrogen bond complexation constants in tetrachloromethane
journal, December 1988

  • Abraham, Michael H.; Grellier, Priscilla L.; Prior, David V.
  • Journal of the American Chemical Society, Vol. 110, Issue 25
  • DOI: 10.1021/ja00233a034

Pivotal Role and Regulation of Proton Transfer in Water Oxidation on Hematite Photoanodes
journal, February 2016

  • Zhang, Yuchao; Zhang, Hongna; Ji, Hongwei
  • Journal of the American Chemical Society, Vol. 138, Issue 8
  • DOI: 10.1021/jacs.5b12069

Electrocatalytic Water Oxidation by a Copper(II) Complex of an Oxidation-Resistant Ligand
journal, April 2017

  • Fisher, Katherine J.; Materna, Kelly L.; Mercado, Brandon Q.
  • ACS Catalysis, Vol. 7, Issue 5
  • DOI: 10.1021/acscatal.7b00494

Density Functional Theory Study of Hydrogen Atom Abstraction from a Series of para -Substituted Phenols: Why is the Hammett σ p + Constant Able to Represent Radical Reaction Rates?
journal, June 2011

  • Yoshida, Tatsusada; Hirozumi, Koji; Harada, Masataka
  • The Journal of Organic Chemistry, Vol. 76, Issue 11
  • DOI: 10.1021/jo200450p

Homogeneous Electrocatalytic Water Oxidation at Neutral pH by a Robust Macrocyclic Nickel(II) Complex
journal, September 2014

  • Zhang, Mei; Zhang, Ming-Tian; Hou, Cheng
  • Angewandte Chemie International Edition, Vol. 53, Issue 48
  • DOI: 10.1002/anie.201406983

Water-soluble hexadentate Schiff-base ligands as sequestrating agents for iron(III) and gallium(III)
journal, January 1988

  • Evans, Dennis F.; Jakubovic, David A.
  • Journal of the Chemical Society, Dalton Transactions, Issue 12
  • DOI: 10.1039/dt9880002927

Reactivity of the copper( iii )-hydroxide unit with phenols
journal, January 2017

  • Dhar, Debanjan; Yee, Gereon M.; Markle, Todd F.
  • Chemical Science, Vol. 8, Issue 2
  • DOI: 10.1039/C6SC03039D

Oxidation of C−H Bonds by [(bpy) 2 (py)Ru IV O] 2+ Occurs by Hydrogen Atom Abstraction
journal, August 2003

  • Bryant, Jasmine R.; Mayer, James M.
  • Journal of the American Chemical Society, Vol. 125, Issue 34
  • DOI: 10.1021/ja035276w

Hydrogen Atom Abstraction from Hydrocarbons by a Copper(III)-Hydroxide Complex
journal, January 2015

  • Dhar, Debanjan; Tolman, William B.
  • Journal of the American Chemical Society, Vol. 137, Issue 3
  • DOI: 10.1021/ja512014z

A Continuum of Proton-Coupled Electron Transfer Reactivity
journal, September 2018

  • Darcy, Julia W.; Koronkiewicz, Brian; Parada, Giovanny A.
  • Accounts of Chemical Research, Vol. 51, Issue 10
  • DOI: 10.1021/acs.accounts.8b00319

Properties of the oxo/aqua system (bpy)2(py)RuO2+/(bpy)2(py)Ru(OH2)2+
journal, February 1981

  • Moyer, Bruce A.; Meyer, Thomas J.
  • Inorganic Chemistry, Vol. 20, Issue 2
  • DOI: 10.1021/ic50216a024

Predicting organic hydrogen atom transfer rate constants using the Marcus cross relation
journal, March 2010

  • Warren, J. J.; Mayer, J. M.
  • Proceedings of the National Academy of Sciences, Vol. 107, Issue 12
  • DOI: 10.1073/pnas.0910347107

Quantum Chemical Modeling of the Oxidation of Dihydroanthracene by the Biomimetic Nonheme Iron Catalyst [(TMC)Fe IV (O)] 2+
journal, August 2007

  • Johansson, Adam Johannes; Blomberg, Margareta R. A.; Siegbahn, Per E. M.
  • The Journal of Physical Chemistry C, Vol. 111, Issue 33
  • DOI: 10.1021/jp0730444
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