Skip to main content
OSTI.GOVU.S. Department of Energy Office of Scientific and Technical Information
U.S. Department of Energy
Office of Scientific and Technical Information
 

Metal–Organic Frameworks as a Tunable Platform to Deconvolute Stereoelectronic Effects on the Catalytic Activity of Thioanisole Oxidation

Journal Article · · Journal of the American Chemical Society
DOI:https://doi.org/10.1021/jacs.3c11809· OSTI ID:2481426
 [1];  [2];  [3];  [4];  [2];  [5];  [2];  [3];  [6];  [2]
  1. Northwestern University, Evanston, IL (United States); Argonne National Laboratory (ANL), Argonne, IL (United States)
  2. Northwestern University, Evanston, IL (United States)
  3. Stony Brook University, NY (United States)
  4. Northwestern University, Evanston, IL (United States); University of Kansas, Lawrence, KS (United States)
  5. Northwestern University, Evanston, IL (United States); Argonne National Laboratory (ANL), Argonne, IL (United States); Lawrence Berkeley National Laboratory (LBNL), Berkeley, CA (United States); University of California, Berkeley, CA (United States)
  6. Argonne National Laboratory (ANL), Argonne, IL (United States); University of Chicago, IL (United States)
+ Show Author Affiliations

The local environment of a metal active site plays an important role in affecting catalytic activity and selectivity. In re-cent studies, tailoring the behavior of a molybdenum-based active site via modulation of the first coordination sphere has led to improved thioanisole oxidation performance, but disentangling electronic effects from steric influences that arise from these modifications is nontrivial, especially in heterogeneous systems. To this end, the tunability of metal–organic frameworks (MOFs) makes them promising scaffolds for controlling the coordination sphere of a heterogene-ous, catalytically-active metal site while offering additional, attractive features such as crystallinity and high porosity. Herein, we report a variety of MOF-supported Mo species, which were investigated for catalytic thioanisole oxidation to methyl phenyl sulfoxide and/or methyl phenyl sulfone using tert-butyl hydroperoxide (tBHP) as the oxidant. In particular, MOFs of contrasting node architectures were targeted, presenting a unique opportunity to investigate ste-reoelectronic control of Mo active sites in a systematic manner. A Zr6-based MOF, NU-1000, was employed along with its sulfated analog Zr6-based NU-1000-SO4 to anchor a dioxymolybdenum species, which enabled examination of sup-port-mediated active site polarizability on catalytic performance. In addition, a MOF containing a mixed metal node, Mo-MFU-4l, was used to probe the stereoelectronic impact of an N-donor ligand environment on the catalytic activity of the transmetalated Mo center. Furthermore, characterization techniques including single crystal X-ray diffraction, were concomi-tantly used with reaction kinetic profiles to better comprehend the dynamics of different Mo active sites, thus correlat-ing structural change with activity.

Research Organization:
University of Chicago, IL (United States); Argonne National Laboratory (ANL), Argonne, IL (United States)
Sponsoring Organization:
USDOE Office of Science (SC), Basic Energy Sciences (BES); National Science Foundation (NSF)
Grant/Contract Number:
SC0023383; AC02-06CH11357
OSTI ID:
2481426
Alternate ID(s):
OSTI ID: 2467577
OSTI ID: 2467578
Journal Information:
Journal of the American Chemical Society, Journal Name: Journal of the American Chemical Society Journal Issue: 6 Vol. 146; ISSN 0002-7863
Publisher:
American Chemical Society (ACS)Copyright Statement
Country of Publication:
United States
Language:
English

References (44)

Acidity Scale for Metal Oxides and Sanderson's Electronegativities of Lanthanide Elements journal December 2008
Molybdenum‐Catalyzed Olefin Epoxidation: Ligand Effects journal May 1997
Unveiling the Activity Origin of Electrocatalytic Oxygen Evolution over Isolated Ni Atoms Supported on a N‐Doped Carbon Matrix journal October 2019
Oxidation of Sulfoxides with Hydroperoxides journal October 1966
From Octahedral to Icosahedral Metal-Organic Polyhedra Assembled from Two Types of Polyoxovanadate Clusters journal February 2019
Rate and Selectivity Control in Thioether and Alkene Oxidation with H 2 O 2 over Phosphonate‐Modified Niobium(V)–Silica Catalysts journal September 2017
Recent Progress and Emerging Technologies towards a Sustainable Synthesis of Sulfones journal October 2021
Formation of Mono Oxo Molybdenum(IV) PNP Pincer Complexes: Interplay between Water and Molecular Oxygen journal February 2018
Modulating the local coordination environment of single-atom catalysts for enhanced catalytic performance journal March 2020
Metal catalysis in oxidation by peroxides part 13. The electrophilic character of the oxygen transfer from peroxomolybdenum(VI) to sulphides journal January 1982
Coordination environment of active sites and their effect on catalytic performance of heterogeneous catalysts journal April 2022
Epoxidation of soybean oil using a homogeneous catalytic system based on a molybdenum (VI) complex journal August 2010
Metal–organic frameworks: A tunable platform to access single-site heterogeneous catalysts journal September 2019
Preparation, structural characterization, and evaluation of ion-exchange behavior of a new polyoxometalate, [Me2NH2]3[Mo12O40S] in separation of carrier-free 90Y from 90Sr journal December 2016
New chiral molybdenum complex catalyzed sulfide oxidation with hydrogen peroxide journal October 2011
Experimental and theoretical studies of new dioxomolybdenum complex: Synthesis, characterization and application as an efficient homogeneous catalyst for the selective sulfoxidation journal November 2021
Bidentate Lewis base adducts of molybdenum(VI): Ligand impact on catalytic performance and stability journal March 2010
A novel tridentate Schiff base dioxo-molybdenum(VI) complex: Synthesis, crystal structure and catalytic performance in green oxidation of sulfides by urea hydrogen peroxide journal March 2009
Selective oxidation of sulfides to sulfoxides and sulfones at room temperature using H2O2 and a Mo(VI) salt as catalyst journal July 2006
Structures of molybdenum silica catalysts reduced by ethanol, and their relations to catalytic oxidation reactions journal June 1999
Molybdenum Oxides versus Molybdenum Sulfides: Geometric and Electronic Structures of Mo 3 X y − (X = O, S and y = 6, 9) Clusters journal March 2011
Oxygen Atom Transfer Reactivity of Molybdenum(VI) Complexes Employing Pyrimidine- and Pyridine-2-thiolate Ligands journal September 2020
Organometallic MFU-4 l (arge) Metal–Organic Frameworks journal July 2019
Metal–Organic Framework Nodes as a Supporting Platform for Tailoring the Activity of Metal Catalysts journal September 2020
Periodic Trends in Highly Dispersed Groups IV and V Supported Metal Oxide Catalysts for Alkene Epoxidation with H 2 O 2 journal August 2015
Selective Oxidation of Thioanisole with Hydrogen Peroxide using Copper Complexes Encapsulated in Zeolite: Formation of a Thermally Stable and Reactive Copper Hydroperoxo Species journal February 2018
Role of Support Lewis Acid Strength in Copper-Oxide-Catalyzed Oxidative Dehydrogenation of Cyclohexane journal July 2018
Enhanced Activity of Heterogeneous Pd(II) Catalysts on Acid-Functionalized Metal–Organic Frameworks journal April 2019
Electrochemical, Spectroscopic, Structural, and Magnetic Characterization of the Reduced and Protonated α-Dawson Anions in [Fe(η5-C5Me5)2]5[HS2Mo18O62]·3HCONMe2·2Et2O and [NBu4]5[HS2Mo18O62]·2H2O1 journal February 2002
X-ray photoelectron spectroscopy of inorganic and organometallic compounds of molybdenum journal May 1975
New Molybdenum Catalysts for Alkyl Olefin Epoxidation. Their Implications for the Mechanism of Oxygen Atom Transfer journal January 2001
Insights into Catalytic Hydrolysis of Organophosphonates at M–OH Sites of Azolate-Based Metal Organic Frameworks journal June 2021
Modulating Chemical Environments of Metal–Organic Framework-Supported Molybdenum(VI) Catalysts for Insights into the Structure–Activity Relationship in Cyclohexene Epoxidation journal February 2022
Sulfated Zirconium Metal–Organic Frameworks as Well-Defined Supports for Enhancing Organometallic Catalysis journal September 2022
Sintering-Resistant Single-Site Nickel Catalyst Supported by Metal–Organic Framework journal February 2016
An Exceptionally Stable Metal–Organic Framework Supported Molybdenum(VI) Oxide Catalyst for Cyclohexene Epoxidation journal October 2016
Discriminating Catalytically Active FeN x Species of Atomically Dispersed Fe–N–C Catalyst for Selective Oxidation of the C–H Bond journal July 2017
A recyclable ionic liquid-oxomolybdenum(vi) catalytic system for the oxidative desulfurization of model and real diesel fuel journal January 2016
Efficient catalytic greenhouse gas-free hydrogen and aldehyde formation from aqueous alcohol solutions journal January 2017
Efficient and selective oxidation of sulfur mustard using singlet oxygen generated by a pyrene-based metal–organic framework journal January 2016
Revisiting the structural homogeneity of NU-1000, a Zr-based metal–organic framework journal January 2018
MOF-enabled confinement and related effects for chemical catalyst presentation and utilization journal January 2022
Sulfoxidation with hydrogen peroxide catalyzed by [SeO4{WO(O2)2}2]2− journal January 2010
Selective oxidation of organic sulfides to sulfoxides using sugar derived cis-dioxo molybdenum(vi) complexes: kinetic and mechanistic studies journal January 2016

Similar Records

Node-Solution Microenvironment Governs the Selectivity of Thioanisole Oxidation within Catalytic Zr-Based Metal–Organic Framework
Journal Article · Fri Jul 18 00:00:00 EDT 2025 · ACS Applied Materials & Interfaces · OSTI ID:2575419

Related Subjects

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY
Anions
Catalysts
Ligands
Metal–Organic Frameworks
Oxidation
Oxides
Transition metals