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

Title: Benzene Selectivity in Competitive Arene Hydrogenation: Effects of Single-Site Catalyst···Acidic Oxide Surface Binding Geometry

Journal Article · · Journal of the American Chemical Society
DOI:https://doi.org/10.1021/jacs.5b03254· OSTI ID:1179606
 [1];  [1];  [2];  [2];  [3];  [4];  [4];  [4];  [5];  [6];  [1];  [1]
  1. Department of Chemistry, Northwestern University, Evanston, Illinois 60208, United States
  2. Exploratory Catalysis Research, UOP LLC, a Honeywell Company, 25 East Algonquin Road, Des Plaines, Illinois 60017, United States
  3. Dipartimento di Chimica, Universita’ degli Studi di Roma “La Sapienza” and INSTM UdR Roma, p.le A. Moro 5, I-00185, Roma, Italy
  4. Chemical Sciences and Engineering Division, Argonne National Laboratory, Argonne, Illinois 60439 United States
  5. U.S. DOE Ames Laboratory, Iowa State University, Ames, Iowa 50011-3020, United States
  6. U.S. DOE Ames Laboratory, Iowa State University, Ames, Iowa 50011-3020, United States, Department of Chemistry, Iowa State University, Ames, Iowa 50011-3020, United States
+ Show Author Affiliations

Organozirconium complexes are chemisorbed on Brønsted acidic sulfated ZrO2 (ZrS), sulfated Al2O3 (AlS), and ZrO2–WO3 (ZrW). Under mild conditions (25 °C, 1 atm H2), the supported Cp*ZrMe3, Cp*ZrBz3, and Cp*ZrPh3 catalysts are very active for benzene hydrogenation with activities declining with decreasing acidity, ZrS >> AlS ≈ ZrW, arguing that more Brønsted acidic oxides (those having weaker corresponding conjugate bases) yield stronger surface organometallic electrophiles and for this reason have higher benzene hydrogenation activity. Benzene selective hydrogenation, a potential approach for carcinogenic benzene removal from gasoline, is probed using benzene/toluene mixtures, and selectivities for benzene hydrogenation vary with catalyst as ZrBz3+/ZrS–, 83% > Cp*ZrMe2+/ZrS–, 80% > Cp*ZrBz2+/ZrS–, 67% > Cp*ZrPh2+/ZrS–, 57%. For Cp*ZrBz2+/ZrS–, which displays the highest benzene hydrogenation activity with moderate selectivity in benzene/toluene mixtures. Other benzene/arene mixtures are examined, and benzene selectivities vary with arene as mesitylene, 99%, > ethylbenzene, 86% > toluene, 67%. Structural and computational studies by solid-state NMR spectroscopy, XAS, and periodic DFT methods applied to supported Cp*ZrMe3 and Cp*ZrBz3 indicate that larger Zr···surface distances are present in more sterically encumbered Cp*ZrBz2+/AlS– vs Cp*ZrMe2+/AlS–. Furthermore, the combined XAS, solid state NMR, and DFT data argue that the bulky catalyst benzyl groups expand the “cationic” metal center–anionic sulfated oxide surface distances, and this separation/weakened ion-pairing enables the activation/insertion of more sterically encumbered arenes and influences hydrogenation rates and selectivity patterns.

Research Organization:
Argonne National Laboratory (ANL), Argonne, IL (United States); Ames Laboratory (AMES), Ames, IA (United States)
Sponsoring Organization:
USDOE Office of Science (SC), Basic Energy Sciences (BES)
Grant/Contract Number:
AC02-06CH11357; FG02-86ER13511; AC02-07CH11358
OSTI ID:
1179606
Alternate ID(s):
OSTI ID: 1214127; OSTI ID: 1234445
Report Number(s):
IS-J-8692
Journal Information:
Journal of the American Chemical Society, Journal Name: Journal of the American Chemical Society Vol. 137 Journal Issue: 21; ISSN 0002-7863
Publisher:
American Chemical SocietyCopyright Statement
Country of Publication:
United States
Language:
English
Citation Metrics:
Cited by: 62 works
Citation information provided by
Web of Science

References (118)

Model Ziegler-Type Hydrogenation Catalyst Precursors, [(1,5-COD)M(μ-O 2 C 8 H 15 )] 2 (M = Ir and Rh): Synthesis, Characterization, and Demonstration of Catalytic Activity En Route to Identifying the True Industrial Hydrogenation Catalysts journal January 2009
Zeolite supported platinum catalysts for benzene hydrogenation and naphthene isomerization journal May 2011
Selective conversion of butane into liquid hydrocarbon fuels on alkane metathesis catalysts journal January 2012
Gamma-alumina: An Active Support to Obtain Immobilized Electron Poor Zr Complexes journal March 2008
Zirconium Hydrocarbyl Chemisorption on Sulfated Metal Oxides:  New Supports, Chemisorption Pathways, and Implications for Catalysis journal October 2004
Alkyl and hydride derivatives of (pentamethylcyclopentadienyl)zirconium(IV) journal June 1982
Molecular nature of support effects in single-site heterogeneous catalysts: silica vs. alumina journal January 2011
Identification of kinetic models of heterogeneously catalyzed reactions journal February 2002
Indirectly detected heteronuclear correlation solid-state NMR spectroscopy of naturally abundant 15N nuclei journal February 2014
Cyclopentadienyl and Olefin Substituent Effects on Insertion and β-Hydrogen Elimination with Group 4 Metallocenes. Kinetics, Mechanism, and Thermodynamics for Zirconocene and Hafnocene Alkyl Hydride Derivatives journal October 2005
Successive Heterolytic Cleavages of H 2 Achieve N 2 Splitting on Silica-Supported Tantalum Hydrides: A DFT Proposed Mechanism journal June 2012
Electron-Deficient Group 4 Metal Complexes of Sulfur-Bridged Dialkoxide Ligands:  Synthesis, Structure, and Polymerization Activity Studies journal September 2005
Highly selective benzene hydrogenation to cyclohexene over supported Ru catalyst without additives journal January 2011
Synthesis, Spectroscopy, and Catalytic Properties of Cationic Organozirconium Adsorbates on “Super Acidic” Sulfated Alumina. “Single-Site” Heterogeneous Catalysts with Virtually 100 Active Sites journal April 2003
Supported Single-Site Organometallic Catalysts for the Synthesis of High-Performance Polyolefins journal November 2014
Exceptionally thermally stable, hydrocarbon soluble Ziegler-type Ir(0)n nanoparticle catalysts made from [Ir(1,5-COD)(μ-O2C8H15)]2 plus AlEt3: Tests of key hypotheses for their unusual stabilization journal November 2013
Synthesis, Characterization, and Heterogeneous Catalytic Implementation of Sulfated Alumina Nanoparticles. Arene Hydrogenation and Olefin Polymerization Properties of Supported Organozirconium Complexes journal February 2011
Understanding Tantalum-Catalyzed Ethylene Trimerization: When Things Go Wrong journal April 2013
On the Fate of Silica-Supported Half-Metallocene Cations: Elucidating a Catalyst’s Deactivation Pathways journal June 2012
Industrial Ziegler-Type Hydrogenation Catalysts Made from Co(neodecanoate) 2 or Ni(2-ethylhexanoate) 2 and AlEt 3 : Evidence for Nanoclusters and Sub-Nanocluster or Larger Ziegler-Nanocluster Based Catalysis journal May 2011
Hafnium-Hydride Complexes Anchored to Silica. Catalysts of the Low Temperature Hydrogenolysis of Alkanes and Hydrogenation of Olefins journal November 1993
NOE and PGSE NMR Spectroscopic Studies of Solution Structure and Aggregation in Metallocenium Ion-Pairs journal February 2004
Homogeneous and Heterogeneous Catalysis: Bridging the Gap through Surface Organometallic Chemistry journal January 2003
Supported Metallocene Catalysts by Surface Organometallic Chemistry. Synthesis, Characterization, and Reactivity in Ethylene Polymerization of Oxide-Supported Mono- and Biscyclopentadienyl Zirconium Alkyl Complexes:  Establishment of Structure/Reactivity Relationships journal April 2001
Adsorption and Photoadsorption States of Benzene Derivatives on Titanium Oxide Studied by NMR journal July 2011
Electron-deficient group IV metal alkyl cations, and the synthesis of Zr(CH 2 Ph) 3 (η 6 -C 6 H 5 )BPh 3 : a fluxional arene π-complex of a d 0 metal journal January 1990
[(SiO)Ta V Cl 2 Me 2 ]: A Well-Defined Silica-Supported Tantalum(V) Surface Complex as Catalyst Precursor for the Selective Cocatalyst-Free Trimerization of Ethylene journal October 2012
Development Plus Kinetic and Mechanistic Studies of a Prototype Supported-Nanoparticle Heterogeneous Catalyst Formation System in Contact with Solution: Ir(1,5-COD)Cl/γ-Al 2 O 3 and Its Reduction by H 2 to Ir(0) n /γ-Al 2 O 3 journal July 2010
Radiative Association Kinetics and Binding Energies of Chromium Ions with Benzene and Benzene Derivatives journal June 1997
Express method for total content assessment of aromatic hydrocarbons and oxygen in finished gasolines by refractometry and densimetry journal February 2015
Ruthenium(0) Nanoclusters Stabilized by a Nanozeolite Framework: Isolable, Reusable, and Green Catalyst for the Hydrogenation of Neat Aromatics under Mild Conditions with the Unprecedented Catalytic Activity and Lifetime journal May 2010
Compensation behaviour in the hydrogenation of benzene, toluene and o-xylene over Ni/SiO2. Determination of true activation energies journal January 1996
Cationic Metallocene Polymerization Catalysts. Synthesis and Properities of the First Base-Free Zirconocene Hydride journal October 1992
Zinc(II) η 1 - and η 2 -Toluene Complexes:  Structure and Bonding in Zn(C 6 F 5 ) 2 ·(toluene) and Zn(C 6 F 4 -2-C 6 F 5 ) 2 ·(toluene) journal July 2006
Hydrocarbon-Soluble, Isolable Ziegler-Type Ir(0) n Nanoparticle Catalysts Made from [(1,5-COD)Ir(μ-O 2 C 8 H 15 )] 2 and 2–5 Equivalents of AlEt 3 : Their High Catalytic Activity, Long Lifetime, and AlEt 3 -Dependent, Exceptional, 200 °C Thermal Stability journal March 2012
Benzene reduction in gasoline by alkylation with olefins: Comparison of Beta and MCM-22 catalysts journal January 2012
Shifting From Ziegler-Natta to Philips-Type Catalyst? A Simple and Safe Access to Reduced Titanium Systems for Ethylene Polymerization journal September 2011
Synthesis, crystal structure, and olefin polymerization activity of a zwitterionic .eta.6-arene zirconium tris(hydrocarbyl) journal February 1993
In Situ Formed “Weakly Ligated/Labile Ligand” Iridium(0) Nanoparticles and Aggregates as Catalysts for the Complete Hydrogenation of Neat Benzene at Room Temperature and Mild Pressures journal June 2010
Highly Variable Zr–CH2–Ph Bond Angles in Tetrabenzylzirconium: Analysis of Benzyl Ligand Coordination Modes journal November 2012
Links Between Single-Site Heterogeneous and Homogeneous Catalysis. DFT Analysis of Pathways for Organozirconium Catalyst Chemisorptive Activation and Olefin Polymerization on γ-Alumina journal November 2008
Alkane Metathesis with the Tantalum Methylidene [(≡SiO)Ta(═CH 2 )Me 2 ]/[(≡SiO) 2 Ta(═CH 2 )Me] Generated from Well-Defined Surface Organometallic Complex [(≡SiO)Ta V Me 4 ] journal January 2015
Surface-bound metal hydrocarbyls. Organometallic connections between heterogeneous and homogeneous catalysis journal February 1992
Doping effects of B in ZrO2 on structural and catalytic properties of Ru/B-ZrO2 catalysts for benzene partial hydrogenation journal March 2014
UOP Platforming leading octane technology into the 1990's journal December 1993
Constraining Asymmetric Organometallic Catalysts within Mesoporous Supports Boosts Their Enantioselectivity journal December 2003
Investigation of active metal species formation in Pd-promoted sulfated zirconia isomerization catalyst journal October 2010
Surface Organometallic Chemistry of Hf(CH 2 t Bu) 4 on Silica and Silica−Alumina: Reaction of the Resulting Grafted Hafnium Neopentyl with Dihydrogen journal March 2010
Catalytic Hydrogenolysis and Isomerization of Light Alkanes over the Silica-Supported Titanium Hydride Complex (⋮SiO) 3 TiH journal December 1997
Supported Organometallics. Highly Electrophilic Cationic Metallocene Hydrogenation and Polymerization Catalysts Formed via Protonolytic Chemisorption on Sulfated Zirconia journal December 1998
Oxo/Imido Heterometathesis Reactions Catalyzed by a Silica-Supported Tantalum Imido Complex journal June 2013
Enantioselective Hydrogenation of Aromatic Ketones Catalyzed by a Mesoporous Silica‐Supported Iridium Catalyst journal July 2008
Cationic Zirconocene Olefin Polymerization Catalysts Based on the Organo-Lewis Acid Tris(pentafluorophenyl)borane. A Synthetic,Structural, Solution Dynamic, and Polymerization Catalytic Study journal November 1994
Hybrid Mesoporous-Silica Materials Functionalized by PtII Complexes: Correlation between the Spatial Distribution of the Active Center, Photoluminescence Emission, and Photocatalytic Activity journal August 2012
Chemisorption Pathways and Catalytic Olefin Polymerization Properties of Group 4 Mono- and Binuclear Constrained Geometry Complexes on Highly Acidic Sulfated Alumina journal April 2009
Learning from the Neighbors: Improving Homogeneous Catalysts with Functional Ligands Motivated by Heterogeneous and Biocatalysis journal February 2012
Catalysis and Surface Organometallic Chemistry: A View from Theory and Simulations journal March 2010
Surface Organozirconium Electrophiles Activated by Chemisorption on “Super Acidic” Sulfated Zirconia as Hydrogenation and Polymerization Catalysts. A Synthetic, Structural, and Mechanistic Catalytic Study journal April 2002
Grafting Reaction of Platinum Organometallic Complexes on Silica-Supported or Unsupported Heteropolyacids journal April 2011
Mesostructured Hybrid Organic–Silica Materials: Ideal Supports for Well-Defined Heterogeneous Organometallic Catalysts journal April 2014
Surface structural-chemical characterization of a single-site d0 heterogeneous arene hydrogenation catalyst having 100% active sites journal December 2012
Revisiting the Metathesis of 13 C-Monolabeled Ethane journal December 2010
Low-Temperature Hydrogenolysis of Alkanes Catalyzed by a Silica-Supported Tantalum Hydride Complex, and Evidence for a Mechanistic Switch from Group IV to Group V Metal Surface Hydride Complexes journal June 2000
C−H Bond Activation and Organometallic Intermediates on Isolated Metal Centers on Oxide Surfaces journal February 2010
A Kinetic Study of Ethylene and 1-Hexene Homo- and Copolymerization Catalyzed by a Silica-Supported Cr(IV) Complex:  Evidence for Propagation by a Migratory Insertion Mechanism journal September 2000
Design Strategies for the Molecular Level Synthesis of Supported Catalysts journal August 2011
Development of the first well-defined tungsten oxo alkyl derivatives supported on silica by SOMC: towards a model of WO3/SiO2 olefin metathesis catalyst journal January 2010
Low temperature hydrogenolysis of waxes to diesel range gasoline and light alkanes: Comparison of catalytic properties of group 4, 5 and 6 metal hydrides supported on silica–alumina journal January 2012
A well-defined silica-supported aluminium alkyl through an unprecedented, consecutive two-step protonolysis–alkyl transfer mechanism journal January 2011
Non-oxidative coupling of methane catalysed by supported tungsten hydride onto alumina and silica–alumina in classical and H2 permeable membrane fixed-bed reactors journal January 2010
Quantitative Investigation of a Hybrid Ziegler–Natta Catalyst Support Prepared by Grafting Di( n ‐butyl)magnesium onto Partially Dehydroxylated Silica journal March 2011
Quantitative 1,10-Phenanthroline Catalyst-Poisoning Kinetic Studies of Rh(0) Nanoparticle and Rh 4 Cluster Benzene Hydrogenation Catalysts: Estimates of the Poison K association Binding Constants, of the Equivalents of Poison Bound and of the Number of Catalytically Active Sites for Each Catalyst journal August 2012
Acidity of Mesoporous MoO x /ZrO 2 and WO x /ZrO 2 Materials:  A Combined Solid-State NMR and Theoretical Calculation Study journal June 2006
Preparation of Group 4B complexes containing tri-tert-butylmethoxide (tritox), a steric cyclopentadienyl equivalent journal July 1984
Organometallic thermochemistry. Metal hydrocarbyl, hydride, halide, carbonyl, amide, and alkoxide bond enthalpy relationships and their implications in pentamethylcyclopentadienyl and cyclopentadienyl complexes of zirconium and hafnium journal November 1988
Synthesis of solid superacid of tungsten oxide supported on zirconia and its catalytic action for reactions of butane and pentane journal January 1988
Is It Homogeneous or Heterogeneous Catalysis Derived from [RhCp*Cl 2 ] 2 ? In Operando XAFS, Kinetic, and Crucial Kinetic Poisoning Evidence for Subnanometer Rh 4 Cluster-Based Benzene Hydrogenation Catalysis journal November 2011
Synthesis, Characterization, and Catalytic Properties of Novel Single-Site and Nanosized Platinum Catalysts journal July 2012
Nonlinear Temperature Behavior of Product Ratios in Selection Processes journal September 1996
Synthesis and Structure of Zirconium and Hafnium Polymerisation Catalysts Stabilised by Very Bulky Aminopyridinato Ligands journal November 2008
Supported organometallic complexes part 39: cationic diamine(ether–phosphine)ruthenium(II) complexes as precursors for the hydrogenation of trans-4-phenyl-3-butene-2-one journal April 2004
Improved Syntheses for the Compounds [(1,5-COD)M(μ-O 2 C 8 H 15 )] 2 (M = Ir, Rh) journal September 2011
Sulfated Tin Oxide Nanoparticles as Supports for Molecule-Based Olefin Polymerization Catalysts journal August 2004
Studies of Organically Functionalized Mesoporous Silicas Using Heteronuclear Solid-State Correlation NMR Spectroscopy under Fast Magic Angle Spinning journal May 2005
Origin of the ZnCl2 Effect on CH3ReO3/γ-Al2O3 in Olefin Metathesis journal June 2012
Preparation of Rhodium Catalysts Supported on Carbon Nanotubes by a Surface Mediated Organometallic Reaction journal February 2003
Sterically Encumbered (Perfluoroaryl) Borane and Aluminate Cocatalysts for Tuning Cation−Anion Ion Pair Structure and Reactivity in Metallocene Polymerization Processes. A Synthetic, Structural, and Polymerization Study journal July 1998
“Hydro‐metathesis” of Olefins: A Catalytic Reaction Using a Bifunctional Single‐Site Tantalum Hydride Catalyst Supported on Fibrous Silica (KCC‐1) Nanospheres journal March 2011
External Surface Catalytic Sites of Surfactant-Tailored Nanomorphic Zeolites for Benzene Isopropylation to Cumene journal January 2013
Quantitative Determination of BTEX and Total Aromatic Compounds in Gasoline by Comprehensive Two-Dimensional Gas Chromatography (GC×GC) journal April 1999
Synthesis, Characterization, and Activity in Ethylene Polymerization of Silica Supported Cationic Cyclopentadienyl Zirconium Complexes journal June 2006
A Silica-Supported Double-Decker Silsesquioxane Provides a Second Skin for the Selective Generation of Bipodal Surface Organometallic Complexes journal October 2012
How to Conceptualize Catalytic Cycles? The Energetic Span Model journal February 2011
Spectroscopically Distinct Sites Present in Methyltrioxorhenium Grafted onto Silica−Alumina, and Their Abilities to Initiate Olefin Metathesis journal July 2007
Pd/Al2O3 catalyst for selective hydrogenation of benzene in benzene–toluene mixture journal March 2009
Agostic Interaction of the Smallest Zirconium Methylidene Hydride: Reproduction of the Distorted Structure Experimentally Observed in Matrix Infrared Spectra journal February 2009
Ziegler-type hydrogenation catalysts made from group 8–10 transition metal precatalysts and AlR3 cocatalysts: A critical review of the literature journal January 2010
Effects of Reformulated Gasoline and Motor Vehicle Fleet Turnover on Emissions and Ambient Concentrations of Benzene journal August 2006
The Surface Structure of Sulfated Zirconia:  Periodic ab Initio Study of Sulfuric Acid Adsorbed on ZrO 2 (101) and ZrO 2 (001) journal December 1998
Indirectly detected through-bond chemical shift correlation NMR spectroscopy in solids under fast MAS: Studies of organic–inorganic hybrid materials journal January 2009
Chemical Shift Correlation NMR Spectroscopy with Indirect Detection in Fast Rotating Solids:  Studies of Organically Functionalized Mesoporous Silicas
  • Wiench, Jerzy W.; Bronnimann, Charles E.; Lin, Victor S. -Y
  • Journal of the American Chemical Society, Vol. 129, Issue 40, p. 12076-12077 https://doi.org/10.1021/ja074746+
journal September 2007
Heterolytic cleavage of ammonia N–H bond by bifunctional activation in silica-grafted single site Ta(V) imido amido surface complex. Importance of the outer sphere NH3 assistance journal January 2011
Benzene Reduction by Alkylation in a Solid Phosphoric Acid Catalyzed Olefin Oligomerization Process journal August 2008
Recent developments in the surface and catalytic chemistry of supported organoactinides journal January 1994
Competitive Hydrogenation of Benzene and Toluene on Palladium and Platinum Catalysts journal July 1996
Polymerization of α-olefins and Hydrogenolysis of the Resulting Polyolefins with Hafnium Hydrides Supported on Silica journal April 2009
Heterogenization of Lanthanum and Neodymium Monophosphacyclopentadienyl Bis(tetramethylaluminate) Complexes onto Periodic Mesoporous Silica SBA-15 journal August 2012
Atom-efficient regioselective 1,2-dearomatization of functionalized pyridines by an earth-abundant organolanthanide catalyst journal October 2014
Surface Structure of Hydroxylated and Sulfated Zirconia. A Periodic Density-Functional Study † journal September 2004
Design and Application of a Hybrid Material Featuring Well-Defined, Tuneable Grafting Sites for Supported Catalysis. journal March 2013
Evidence for Metal–Surface Interactions and Their Role in Stabilizing Well-Defined Immobilized Ru–NHC Alkene Metathesis Catalysts journal February 2013
Probing chemistry and kinetics of reactions in heterogeneous catalysts journal January 2013
New Experimental and Theoretical Relation to Determine the Research Octane Number (Ron) of Authentic Aromatic Hydrocarbons Could be Present in the Gasoline Fraction journal June 1999
Molecular Metal Catalysts on Supports: Organometallic Chemistry Meets Surface Science journal July 2014
Mechanistic aspects of dinitrogen cleavage and hydrogenation to produce ammonia in catalysis and organometallic chemistry: relevance of metal hydride bonds and dihydrogen journal January 2014
An investigation of catalyst/cocatalyst/support interactions in silica-supported olefin polymerization catalysts based on Cp*TiMe3* journal May 2005
Iridium Ziegler-Type Hydrogenation Catalysts Made from [(1,5-COD)Ir(μ-O 2 C 8 H 15 )] 2 and AlEt 3 : Spectroscopic and Kinetic Evidence for the Ir n Species Present and for Nanoparticles as the Fastest Catalyst journal September 2010
Conformations of Silica-Bound (Pentafluorophenyl)propyl Groups Determined by Solid-State NMR Spectroscopy and Theoretical Calculations journal September 2010

Similar Records

Mechanistic Insights into C–H Borylation of Arenes with Organoiridium Catalysts Embedded in a Microporous Metal–Organic Framework
Journal Article · Mon Mar 30 00:00:00 EDT 2020 · Organometallics · OSTI ID:1179606
+7 more
Supported organoactinide complexes as heterogeneous catalysts. A kinetic and mechanistic study of facile arene hydrogenation
Journal Article · Wed Dec 16 00:00:00 EST 1992 · Journal of the American Chemical Society; (United States) · OSTI ID:1179606
Rapid reduction of nitric oxide to dinitrogen by zirconium(II): Kinetic studies on a reaction controlled by gas-liquid transport
Journal Article · Wed Sep 15 00:00:00 EDT 1999 · Journal of the American Chemical Society · OSTI ID:1179606

Related Subjects

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY