skip to main content
OSTI.GOV title logo U.S. Department of Energy
Office of Scientific and Technical Information

Title: Operando XAFS Studies on Rh(CAAC)-Catalyzed Arene Hydrogenation

Journal Article · · ACS Catalysis
 [1]; ORCiD logo [1]; ORCiD logo [1];  [2];  [1]; ORCiD logo [1]
  1. Pacific Northwest National Lab. (PNNL), Richland, WA (United States)
  2. Argonne National Lab. (ANL), Argonne, IL (United States)
+ Show Author Affiliations

Rh K-edge X-ray absorption fine structure (XAFS) spectroscopy was used to examine the Rh-catalyzed arene hydrogenation of diphenyl ether by a combination of stoichiometric reactions of [(CAACCy,Dipp)Rh(COD)Cl] (Rh–Cl) (CAACCy,Dipp = cyclic alkyl amino carbene) and operando XAFS kinetics studies. Our results unequivocally show that Rh nanoparticles, generated from the single-site Rh complex Rh–Cl, catalyze the arene hydrogenation. Operando XAFS studies illuminate the role of silver cation on the precatalyst reactivity, the effect of increasing H2 pressure on increasing the catalytic efficiency, the stabilizing influence of Ph2O on the relative rate of formation of active Rh nanoparticles, and the absence of soluble single-site Rh species that might leach from bulk heterogeneous Rh nanoparticles. We gained insights into the divergent deactivation pathways mediated by substoichiometric benzothiophene and excess KOtBu toward H2 activation, which is a key step en route to Rh nanoparticles for arene hydrogenation. Excess KOtBu leads to the formation of a Rh–OtBu complex that interferes with H2 activation, precluding the formation of Rh nanoparticles. Here, benzothiophene does not interfere with the activation of H2 at Rh in the CAACCy,Dipp complex while Rh nanoparticles are formed. Once Rh nanoparticles are formed, however, benzothiophene binds irreversibly to the Rh nanoparticles, preventing the adsorption of H2 and diphenyl ether for arene hydrogenation.

Research Organization:
Argonne National Lab. (ANL), Argonne, IL (United States)
Sponsoring Organization:
USDOE Office of Science (SC), Basic Energy Sciences (BES)
Grant/Contract Number:
AC02-06CH11357
OSTI ID:
1530417
Journal Information:
ACS Catalysis, Vol. 9, Issue 5; ISSN 2155-5435
Publisher:
American Chemical Society (ACS)Copyright Statement
Country of Publication:
United States
Language:
English
Citation Metrics:
Cited by: 33 works
Citation information provided by
Web of Science

References (81)

Recent advances in chemical dearomatization of nonactivated arenes journal January 2018
Catalytic Asymmetric Dearomatization Reactions journal December 2012
Transition-Metal-Mediated Dearomatization Reactions journal July 2000
Group 6 Dihapto-Coordinate Dearomatization Agents for Organic Synthesis journal October 2017
Selective Arene Hydrogenation for Direct Access to Saturated Carbo- and Heterocycles journal April 2019
Privileged chiral N-heterocyclic carbene ligands for asymmetric transition-metal catalysis journal January 2017
N-Heterocyclic Carbenes in Asymmetric Hydrogenation journal August 2016
Highly Selective Hydrogenation of Aromatic Ketones and Phenols Enabled by Cyclic (Amino)(alkyl)carbene Rhodium Complexes journal July 2015
Hydrogenation of fluoroarenes: Direct access to all- cis -(multi)fluorinated cycloalkanes journal August 2017
Complete Hydrodehalogenation of Polyfluorinated and Other Polyhalogenated Benzenes under Mild Catalytic Conditions journal May 2013
Hydrodefluorination and Hydrogenation of Fluorobenzene under Mild Aqueous Conditions journal August 2012
Hydrodefluorination of fluorobenzene catalyzed by rhodium metal prepared from [Rh(COD)2]+BF4− and supported on SiO2 and Pd-SiO2 journal January 2004
Hydrodefluorination of Fluorobenzene and 1,2-Difluorobenzene under Mild Conditions over Rhodium Pyridylphosphine and Bipyridyl Complexes Tethered on a Silica-Supported Palladium Catalyst journal May 1999
The formation of all-cis-(multi)fluorinated piperidines by a dearomatization–hydrogenation process journal January 2019
Silylarene Hydrogenation: A Strategic Approach that Enables Direct Access to Versatile Silylated Saturated Carbo‐ and Heterocycles journal July 2018
Hydrogenation of Borylated Arenes journal May 2019
Rh(CAAC)-Catalyzed Arene Hydrogenation: Evidence for Nanocatalysis and Sterically Controlled Site-Selective Hydrogenation journal July 2018
Carbene Ligands in Surface Chemistry: From Stabilization of Discrete Elemental Allotropes to Modification of Nanoscale and Bulk Substrates journal September 2015
Nanoclusters in Ionic Liquids:  Evidence for N -Heterocyclic Carbene Formation from Imidazolium-Based Ionic Liquids Detected by 2 H NMR journal April 2005
N-Heterocyclic carbene coated metal nanoparticles journal January 2009
Ballbot-type motion of N-heterocyclic carbenes on gold surfaces journal October 2016
Elucidating the Binding Modes of N-Heterocyclic Carbenes on a Gold Surface journal September 2018
Ruthenium Nanoparticles Stabilized by N-Heterocyclic Carbenes: Ligand Location and Influence on Reactivity journal October 2011
Organometallic Ruthenium Nanoparticles: Synthesis, Surface Chemistry, and Insights into Ligand Coordination journal January 2018
N-Heterocyclic-Carbene-Treated Gold Surfaces in Pentacene Organic Field-Effect Transistors: Improved Stability and Contact at the Interface journal March 2018
Versatile Micropatterns of N-Heterocyclic Carbenes on Gold Surfaces: Increased Thermal and Pattern Stability with Enhanced Conductivity journal July 2018
Stabilization of High Oxidation State Upconversion Nanoparticles by N-Heterocyclic Carbenes journal March 2017
N-Heterocyclic carbene-stabilized gold nanoparticles and their assembly into 3D superlattices journal January 2009
Ultra stable self-assembled monolayers of N-heterocyclic carbenes on gold journal March 2014
Ultrastable Gold Nanoparticles Modified by Bidentate N -Heterocyclic Carbene Ligands journal January 2018
Modular Bidentate Hybrid NHC-Thioether Ligands for the Stabilization of Palladium Nanoparticles in Various Solvents journal April 2016
Negatively Charged N-Heterocyclic Carbene-Stabilized Pd and Au Nanoparticles and Efficient Catalysis in Water journal August 2015
Long-chain NHC-stabilized RuNPs as versatile catalysts for one-pot oxidation/hydrogenation reactions journal January 2016
Molecular Adsorbates Switch on Heterogeneous Catalysis: Induction of Reactivity by N-Heterocyclic Carbenes journal June 2017
Asymmetric Nanocatalysis: N-Heterocyclic Carbenes as Chiral Modifiers of Fe3O4/Pd nanoparticles journal September 2010
A Molecular Surface Functionalization Approach to Tuning Nanoparticle Electrocatalysts for Carbon Dioxide Reduction journal June 2016
Chelating N-Heterocyclic Carbene Ligands Enable Tuning of Electrocatalytic CO 2 Reduction to Formate and Carbon Monoxide: Surface Organometallic Chemistry journal March 2018
A New Mode of Operation of Pd-NHC Systems Studied in a Catalytic Mizoroki–Heck Reaction journal April 2017
Fast and Slow Release of Catalytically Active Species in Metal/NHC Systems Induced by Aliphatic Amines journal April 2018
Stable crystalline annulated diaminocarbenes: coordination with rhodium(i), iridium(i) and catalytic hydroformylation studies journal January 2009
Anionic N-Heterocyclic Carbenes with N,N′-Bis(fluoroaryl) and N,N′-Bis(perfluoroaryl) Substituents journal October 2010
A cationic rhodium(I) N-heterocyclic carbene complex isolated as an aqua adduct journal August 2011
Synthesis and Structure of Silver and Rhodium 1,2,3-Triazol-5-ylidene Mesoionic Carbene Complexes journal December 2011
N-Heterocyclic Carbene Complexes of Rhodium and Iridium: Steric Effects on Molecular Conformation journal October 2009
Transfer Hydrogenation of Imines and Alkenes and Direct Reductive Amination of Aldehydes Catalyzed by Triazole-Derived Iridium(I) Carbene Complexes journal February 2007
Cationic Iridium Complexes Bearing Imidazol-2-ylidene Ligands as Transfer Hydrogenation Catalysts journal August 2001
A Cationic Iridium Complex Bearing an Imidazol-2-ylidene Ligand as Alkene Hydrogenation Catalyst journal February 2001
In-Depth Study on Chloride Abstractions from (NHC)Ir(COD)Cl Complexes journal February 2017
Iridium(I) Hydroxides: Powerful Synthons for Bond Activation journal April 2013
Asymmetric Hydrogenation of Enamides with Rh-BisP* and Rh-MiniPHOS Catalysts. Scope, Limitations, and Mechanism journal June 2001
Challenging the Major/Minor Concept in Rh-Catalyzed Asymmetric Hydrogenation journal March 2015
Investigating the Kinetics of Homogeneous Hydrogenation Reactions Using PHIP NMR Spectroscopy journal June 1999
In situ Transfer of Parahydrogen-Induced Nuclear Spin Polarization—Structural Characterization of Hydrogenation Intermediates journal October 2000
Rhodium catalyzed hydrogenation reactions in aqueous micellar systems as green solvents journal January 2011
Investigations into the Formation and Stability of Cationic Rhodium Diphosphane η 6 -Arene Complexes journal August 2012
The Inhibiting Influence of Aromatic Solvents on the Activity of Asymmetric Hydrogenations We would like to thank the Deutsche Forschungsgemeinschaft as well as the Fonds der Chemischen Industrie for their generous support of this work. We are also indebted to Prof. Dr. U. Rosenthal and Dr. D. Selent for helpful discussions. Franz Hein prepared bis(η6-arene)-chromium(I)-complex cations already in 1919; their true structure as hexahapto complexes was only realized more than 35 years later. journal March 2002
Highly Efficient Asymmetric Synthesis of β-Amino Acid Derivatives via Rhodium-Catalyzed Hydrogenation of β-(Acylamino)acrylates journal September 1999
Pressure Dependent Highly Enantioselective Hydrogenation of Unsaturated β-Amino Acid Precursors journal September 2001
Rh−DuPHOS-Catalyzed Enantioselective Hydrogenation of Enol Esters. Application to the Synthesis of Highly Enantioenriched α-Hydroxy Esters and 1,2-Diols journal May 1998
Homogeneous catalysis of arene hydrogenation by cationic rhodium arene complexes journal July 1983
Novel coordination chemistry and catalytic properties of cationic 1,2-bis(diphenylphosphino)ethanerhodium(I) complexes journal November 1977
Cationic Rhodium-BINAP Complexes: Full Characterization of Solvate- and Arene-Bridged Dimeric Species journal October 2011
A Two-Coordinate Nickel Imido Complex That Effects C−H Amination journal February 2011
Mechanistic Investigations of the Hydrogenolysis of Diaryl Ethers Catalyzed by Nickel Complexes of N -Heterocyclic Carbene Ligands journal November 2017
One-Pot, Single-Step, and Gram-Scale Synthesis of Mononuclear [(η 6 -arene)Ni(N-heterocyclic carbene)] Complexes: Useful Precursors of the Ni 0 –NHC Unit journal February 2014
Taming a monomeric [Cu(η 6 -C 6 H 6 )] + complex with silylene journal January 2018
Labile Rhodium(I)–N-Heterocyclic Carbene Complexes journal April 2013
Hydride-Rhodium(III)-N-Heterocyclic Carbene Catalysts for Vinyl-Selective H/D Exchange: A Structure-Activity Study journal June 2014
Hydrogenation and hydrogenolysis of thiophenic molecules catalysed by soluble metal complexes journal January 1996
Ruthenium, rhodium, and iridium complexes of .pi.-bound thiophene and benzo[b]thiophenes: models for thiophene binding to HDS catalysts journal March 1988
Sulfur versus 2,3-.eta.2 coordination of benzo[b]thiophene (BT) in Cp'(CO)2Re(BT) journal May 1991
The benzo[b]thiophene (BT) rhenium complexes Cp'(CO)2Re(BT): models for BT adsorption on hydrodesulfurization catalysts journal October 1992
Equilibrium studies of the displacement of .eta.1-(S)-thiophenes (Th) from Cp(CO)(PPh3)Ru(.eta.1-(S)-Th)+ journal February 1992
Synthesis and protonation of the bridging benzo[b]thiophene (BT) complexes [Cp'(CO)2Re](.eta.2:.eta.1(S)-.mu.2-BT)[Re(CO)2Cp''] journal January 1994
Coordination and Oxidative Addition at a Low-Coordinate Rhodium(I)β-Diiminate Centre journal March 2002
Understanding active species in catalytic transformations: From molecular catalysis to nanoparticles, leaching, “Cocktails” of catalysts and dynamic systems journal September 2017
Full-Range Interconversion of Nanocrystals and Bulk Metal with a Highly Selective Molecular Catalyst journal May 2018
On the Nature of the Active Species in Palladium Catalyzed Mizoroki–Heck and Suzuki–Miyaura Couplings – Homogeneous or Heterogeneous Catalysis, A Critical Review journal April 2006
Monomolecular, nanosized and heterogenized palladium catalysts for the Heck reaction journal May 2007
Visual Observation of Redistribution and Dissolution of Palladium during the Suzuki–Miyaura Reaction journal April 2008
Studies on the catalytic ability of palladium wire, foil and sponge in the Suzuki–Miyaura cross-coupling journal September 2011

Cited By (3)

The debut of chiral cyclic (alkyl)(amino)carbenes (CAACs) in enantioselective catalysis journal January 2019
Accessing Difluoromethylated and Trifluoromethylated cis ‐Cycloalkanes and Saturated Heterocycles: Preferential Hydrogen Addition to the Substitution Sites for Dearomatization journal November 2019
Accessing Difluoromethylated and Trifluoromethylated cis -Cycloalkanes and Saturated Heterocycles: Preferential Hydrogen Addition to the Substitution Sites for Dearomatization journal October 2019

Similar Records

Related Subjects

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY
Rh(CAAC)
arene hydrogenation
benzothiophene poisoning
cationic rhodium
operando XAFS
rhodium nanoparticles