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Title: Proton or Metal? The H/D Exchange of Arenes in Acidic Solvents

Journal Article · · ACS Catal.
DOI:https://doi.org/10.1021/cs501620f· OSTI ID:1210768

Research Organization:
Energy Frontier Research Centers (EFRC) (United States). Center for Catalytic Hydrocarbon Functionalization (CCHF)
Sponsoring Organization:
USDOE Office of Science (SC), Basic Energy Sciences (BES)
DOE Contract Number:
SC0001298
OSTI ID:
1210768
Journal Information:
ACS Catal., Vol. 5; Related Information: CCHF partners with University of Virginia (lead); Brigham Young University; California Institute of Technology; Colorado School of Mines; University of Maryland; University of North Carolina, Chapel Hill; University of North Texas; Princeton University; The Scripps Research Institute; Yale University
Country of Publication:
United States
Language:
English

References (87)

Iridium-Catalyzed H/D Exchange into Organic Compounds in Water journal March 2002
Exceptionally Low-Temperature Carbon−Hydrogen/Carbon−Deuterium Exchange Reactions of Organic and Organometallic Compounds Catalyzed by the Cp*(PMe 3 )IrH(ClCH 2 Cl) + Cation journal June 2001
H/D Exchange at Aromatic and Heteroaromatic Hydrocarbons Using D2O as the Deuterium Source and Ruthenium Dihydrogen Complexes as the Catalyst journal March 2007
The kinetics of hydrogen isotope exchange in benzene using a homogeneous platinum catalyst journal May 1968
Using Deuterium in Drug Discovery: Leaving the Label in the Drug journal December 2013
Isotope Effects in C−H Bond Activation Reactions by Transition Metals journal February 2003
On the Interpretation of Deuterium Kinetic Isotope Effects in CH Bond Functionalizations by Transition-Metal Complexes journal March 2012
Kinetic Isotope Effects in the Study of Organometallic Reaction Mechanisms journal August 2011
Palladium-Catalyzed ortho -Selective CH Deuteration of Arenes: Evidence for Superior Reactivity of Weakly Coordinated Palladacycles journal November 2013
Palladium-Catalyzed Acetoxylation of Arenes by Novel Sulfinyl N-Heterocyclic Carbene Ligand Complexes journal November 2013
High-Yielding, Versatile, and Practical [Rh(III)Cp*]-Catalyzed Ortho Bromination and Iodination of Arenes journal May 2012
C–H Bond Functionalization of Benzoic Acid: Catalytic Synthesis of 2-Hydroxy-6 H -benzo[ c ]chromen-6-ones Using (Cp*IrCl 2 ) 2 journal September 2011
Effect of Ancillary Ligands and Solvents on H/D Exchange Reactions Catalyzed by Cp*Ir Complexes journal June 2010
Benzene C−H Bond Activation in Carboxylic Acids Catalyzed by O-Donor Iridium(III) Complexes: An Experimental and Density Functional Study journal January 2010
Catalysis of aromatic hydrogen-deuterium exchange by metal hydrides journal August 1970
Arene C–H activation using Rh( i ) catalysts supported by bidentate nitrogen chelates journal January 2015
Activation of C−H Bonds by Metal Complexes journal December 1997
Homogeneous catalysis in the oxidative functionalization of alkanes in protic media journal April 2011
Activation and Oxidative Functionalization of Alkanes by Metal Complexes in Protic Media 1 journal May 2004
Mechanistic Aspects of C−H Activation by Pt Complexes journal June 2005
Organometallic alkane CH activation journal November 2004
Understanding and exploiting C–H bond activation journal May 2002
A Mercury-Catalyzed, High-Yield System for the Oxidation of Methane to Methanol journal January 1993
Platinum Catalysts for the High-Yield Oxidation of Methane to a Methanol Derivative journal April 1998
C−H Bond Activation by Cationic Platinum(II) Complexes:  Ligand Electronic and Steric Effects journal February 2002
Catalytic CH Bond Activation at Nanoscale Lewis Acidic Aluminium Fluorides: H/D Exchange Reactions at Aromatic and Aliphatic Hydrocarbons journal November 2011
Activation of small alkanes on strong solid acids: mechanistic approaches journal November 1997
Main-Group Compounds Selectively Oxidize Mixtures of Methane, Ethane, and Propane to Alcohol Esters journal March 2014
Pt-catalyzed oxidative carbonylation of methane to acetic acid in sulfuric acid journal November 2006
Direct oxidation of methane to acetic acid catalyzed by Pd2+ and Cu2+ in the presence of molecular oxygen journal January 2004
Reactions of hydrocarbons with electrophilic transition metal complexes in trifluoroacetic acid journal February 1994
Direct and Remarkably Efficient Conversion of Methane into Acetic Acid Catalyzed by Amavadine and Related Vanadium Complexes. A Synthetic and a Theoretical DFT Mechanistic Study journal August 2007
Copper- and vanadium-catalyzed methane oxidation into oxygenates with in situ generated H2O2 over Pd/C journal July 2003
Manganese oxide catalyzed methane partial oxidation in trifluoroacetic acid: Catalysis and kinetic analysis journal February 2009
Heterolytic CH Activation with a Cyclometalated Platinum(II) 6-Phenyl-4,4‘-di- tert -butyl-2,2-Bipyridine Complex journal September 2006
New Catalyst Systems for the Catalytic Conversion of Methane into Methanol journal May 2002
Cobalt-Catalyzed Oxidation of Methane to Methyl Trifluoroacetate by Dioxygen journal July 2013
Propane Activation by Palladium Complexes with Chelating Bis(NHC) Ligands and Aerobic Cooxidation journal January 2014
Selective Monooxidation of Light Alkanes Using Chloride and Iodate journal May 2014
Oxidative carbonylation of methane in the presence of Rh complexes in aqueous acetic acid journal March 1998
Cationic Platinum(II) Carboxylato Complexes Are Competent in Catalytic Arene C−H Activation under Mild Conditions journal June 2004
Cationic Palladium(II) Catalysis: C−H Activation/Suzuki−Miyaura Couplings at Room Temperature journal March 2010
Cationic Pd(II)-Catalyzed Fujiwara−Moritani Reactions at Room Temperature in Water journal April 2010
Agostic interactions in transition metal compounds journal April 2007
Palladium(II)-Catalyzed CH Activation/CC Cross-Coupling Reactions: Versatility and Practicality journal June 2009
C–H activation in strongly acidic media. The co-catalytic effect of the reaction medium journal January 2009
Ligand Lone-Pair Influence on Hydrocarbon C−H Activation: A Computational Perspective journal December 2010
Electrophilic, Ambiphilic, and Nucleophilic C−H Bond Activation: Understanding the Electronic Continuum of C−H Bond Activation Through Transition-State and Reaction Pathway Interaction Energy Decompositions journal December 2010
Methane CH Activation by Palladium Complexes with Chelating Bis(NHC) Ligands: A DFT Study journal June 2013
Role of N -Acyl Amino Acid Ligands in Pd(II)-Catalyzed Remote C–H Activation of Tethered Arenes journal January 2014
Structure Activity Relationship Study of Diimine Pt II Catalysts for H/D Exchange journal February 2012
Quantitative Assay for the Direct Comparison of Platinum Catalysts in Benzene H/D Exchange journal September 2009
Catalytic Arene H/D Exchange with Novel Rhodium and Iridium Complexes journal February 2012
Platinum(II) Complexes Containing Quaternized Nitrogen Ligands: Synthesis, Stability, and Evaluation as Catalysts for Methane and Benzene H/D Exchange journal December 2009
Thermal C−H Bond Activation of Benzene, Toluene, and Methane with Cationic [M(X)(bipy)] + (M = Ni, Pd, Pt; X = CH 3 , Cl; bipy = 2,2′-bipyridine): A Mechanistic Study journal March 2011
Platinum and Palladium Complexes Containing Cationic Ligands as Catalysts for Arene H/D Exchange and Oxidation journal July 2010
Effect of Solvent and Ancillary Ligands on the Catalytic H/D Exchange Reactivity of Cp*Ir III (L) Complexes journal September 2013
Rh(III) Pyridinium Substituted Bipyridine Complexes as Catalysts for Arene H/D Exchange journal June 2012
Palladium-Catalyzed Olefin Dioxygenation journal March 2008
The Nature of the Catalytically Active Species in Olefin Dioxygenation with PhI(OAc) 2 : Metal or Proton? journal March 2011
Novel Pd(II)- and Pt(II)-Catalyzed Regio- and Stereoselective trans -Hydroarylation of Alkynes by Simple Arenes journal August 2000
Mechanistic Studies of Fujiwara Hydroarylation. C−H Activation versus Electrophilic Aromatic Substitution journal December 2005
Disambiguation of Metal and Brønsted Acid Catalyzed Pathways for Hydroarylation with Platinum(II) Catalysts journal March 2011
Hydroamination and Hydroalkoxylation Catalyzed by Triflic Acid. Parallels to Reactions Initiated with Metal Triflates journal August 2006
Electrophilic Hydrogen Isotope Substitutions. I. Benzene and Toluene journal December 1958
Superelectrophilic Solvation journal February 2004
H-D exchange of complex acids with aromatic hydrocarbons journal January 1976
Activation, isomerization and H/D exchange of small alkanes in triflic acid journal November 1998
Equilibrium Acidities of Superacids journal January 2011
Assessing the acid strength of solid acid catalysts with the use of linear free energy relationship: H/D exchange with substituted benzene derivatives journal June 2007
Methods for Characterizing Zeolite Acidity journal May 1995
A Unified pH Scale for All Phases journal August 2010
Acid strength of solids probed by catalytic isobutane conversion journal August 2010
The M06 suite of density functionals for main group thermochemistry, thermochemical kinetics, noncovalent interactions, excited states, and transition elements: two new functionals and systematic testing of four M06-class functionals and 12 other functionals journal July 2007
Density‐functional thermochemistry. III. The role of exact exchange journal April 1993
Development of the Colle-Salvetti correlation-energy formula into a functional of the electron density journal January 1988
Ab Initio Calculation of Vibrational Absorption and Circular Dichroism Spectra Using Density Functional Force Fields journal November 1994
Accurate spin-dependent electron liquid correlation energies for local spin density calculations: a critical analysis journal August 1980
Self-consistent molecular orbital methods. 21. Small split-valence basis sets for first-row elements journal January 1980
Self‐consistent molecular orbital methods. XXIII. A polarization‐type basis set for second‐row elements journal October 1982
Jaguar: A high-performance quantum chemistry software program with strengths in life and materials sciences journal July 2013
6-31G * basis set for atoms K through Zn journal July 1998
6-31G* basis set for third-row atoms journal January 2001
A Quantum Mechanical Investigation of the Orientation of Substituents in Aromatic Molecules journal April 1942
Iron(III) acetates journal December 1978
Synthesis and structural characterization of novel bridged platinum(II) biscarbene complexes journal October 2002
Homoleptic chelating N-heterocyclic carbene complexes of palladium and nickel journal February 1999

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Gold(I)-Catalysed Asymmetric Hydroamination of Alkenes: A Silver- and Solvent-Dependent Enantiodivergent Reaction journal June 2017
C−H Functionalisation for Hydrogen Isotope Exchange journal February 2018
Highlights of aliphatic C(sp 3 )-H hydrogen isotope exchange reactions journal August 2019
Fe(OTf) 3 -catalysed Friedel–Crafts reaction of benzenoid arenes with α,β-unsaturated carbonyl compounds: easy access to 1,1-diarylalkanes journal October 2017
Calcium(II)-Catalyzed Intermolecular Hydroarylation of Deactivated Styrenes in Hexafluoroisopropanol journal October 2018
Gold( i ) catalysed regio- and stereoselective intermolecular hydroamination of internal alkynes: towards functionalised azoles journal January 2019
New Trends in Oxidative Functionalization of Carbon–Hydrogen Bonds: A Review journal March 2016
Calcium(II)-Catalyzed Intermolecular Hydroarylation of Deactivated Styrenes in Hexafluoroisopropanol journal October 2018
Nucleophilic Aromatic Substitution at Benzene with Powerful Strontium Hydride and Alkyl Complexes journal February 2019
Highlights of aliphatic C(sp3)-H Hydrogen Isotope Exchange Reactions text January 2019