Evidence for Dynamic Chemical Kinetics at Individual Molecular Ruthenium Catalysts

Easter, Quinn T.; Blum, Suzanne A.

doi:10.1002/ange.201711314

Title: Evidence for Dynamic Chemical Kinetics at Individual Molecular Ruthenium Catalysts

Journal Article · 09 January 2018 · Angewandte Chemie

DOI: https://doi.org/10.1002/ange.201711314 · OSTI ID:1416405

Easter, Quinn T. ^[1];

^[1]

Department of Chemistry University of California, Irvine Irvine CA 92697-2025 USA

Abstract Catalytic cycles are typically depicted as possessing time‐invariant steps with fixed rates. Yet the true behavior of individual catalysts with respect to time is unknown, hidden by the ensemble averaging inherent to bulk measurements. Evidence is presented for variable chemical kinetics at individual catalysts, with a focus on ring‐opening metathesis polymerization catalyzed by the second‐generation Grubbs’ ruthenium catalyst. Fluorescence microscopy is used to probe the chemical kinetics of the reaction because the technique possesses sufficient sensitivity for the detection of single chemical reactions. Insertion reactions in submicron regions likely occur at groups of many (not single) catalysts, yet not so many that their unique kinetic behavior is ensemble averaged.

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Sponsoring Organization:: USDOE

Grant/Contract Number:: SC0016467

OSTI ID:: 1416405

Journal Information:: Angewandte Chemie, Journal Name: Angewandte Chemie Journal Issue: 6 Vol. 130; ISSN 0044-8249

Publisher:: Wiley Blackwell (John Wiley & Sons)Copyright Statement

Country of Publication:: Germany

Language:: English

References (33)

Chemische Bildgebung von räumlichen Heterogenitäten in katalytischen Festkörpern auf unterschiedlichen Längen- und Zeitskalen Weckhuysen, Bert M. Angewandte Chemie, Vol. 121, Issue 27 https://doi.org/10.1002/ange.200900339	journal	June 2009
Funktionale Blockcopolymere: nanostrukturierte Materialien mit neuen Anwendungsmöglichkeiten Schacher, Felix H.; Rupar, Paul A.; Manners, Ian Angewandte Chemie, Vol. 124, Issue 32 https://doi.org/10.1002/ange.201200310	journal	July 2012
Direkte Beobachtung alternativer Reaktionswege an einzelnen Molekülen Rybina, Arina; Lang, Carolin; Wirtz, Marcel Angewandte Chemie, Vol. 125, Issue 24 https://doi.org/10.1002/ange.201300100	journal	April 2013
High-Resolution Single-Molecule Fluorescence Imaging of Zeolite Aggregates within Real-Life Fluid Catalytic Cracking Particles Ristanović, Zoran; Kerssens, Marleen M.; Kubarev, Alexey V. Angewandte Chemie, Vol. 127, Issue 6 https://doi.org/10.1002/ange.201410236	journal	December 2014
Single Turnover at Molecular Polymerization Catalysts Reveals Spatiotemporally Resolved Reactions Easter, Quinn T.; Blum, Suzanne A. Angewandte Chemie, Vol. 129, Issue 44 https://doi.org/10.1002/ange.201708284	journal	September 2017
Chemical Imaging of Spatial Heterogeneities in Catalytic Solids at Different Length and Time Scales Weckhuysen, Bert M. Angewandte Chemie International Edition, Vol. 48, Issue 27 https://doi.org/10.1002/anie.200900339	journal	June 2009
Functional Block Copolymers: Nanostructured Materials with Emerging Applications Schacher, Felix H.; Rupar, Paul A.; Manners, Ian Angewandte Chemie International Edition, Vol. 51, Issue 32 https://doi.org/10.1002/anie.201200310	journal	July 2012
Distinguishing Alternative Reaction Pathways by Single-Molecule Fluorescence Spectroscopy Rybina, Arina; Lang, Carolin; Wirtz, Marcel Angewandte Chemie International Edition, Vol. 52, Issue 24 https://doi.org/10.1002/anie.201300100	journal	April 2013
High-Resolution Single-Molecule Fluorescence Imaging of Zeolite Aggregates within Real-Life Fluid Catalytic Cracking Particles Ristanović, Zoran; Kerssens, Marleen M.; Kubarev, Alexey V. Angewandte Chemie International Edition, Vol. 54, Issue 6 https://doi.org/10.1002/anie.201410236	journal	December 2014
Single Turnover at Molecular Polymerization Catalysts Reveals Spatiotemporally Resolved Reactions Easter, Quinn T.; Blum, Suzanne A. Angewandte Chemie International Edition, Vol. 56, Issue 44 https://doi.org/10.1002/anie.201708284	journal	September 2017
Noninvasive Nanoscopy Uncovers the Impact of the Hierarchical Porous Structure on the Catalytic Activity of Single Dealuminated Mordenite Crystals Kubarev, Alexey V.; Janssen, Kris P. F.; Roeffaers, Maarten B. J. ChemCatChem, Vol. 7, Issue 22 https://doi.org/10.1002/cctc.201500708	journal	August 2015
Principles of Fluorescence Spectroscopy Lakowicz, Joseph R. Springer New York, NY https://doi.org/10.1007/978-0-387-46312-4	book	January 2006
Industrial applications of olefin metathesis Mol, J. Journal of Molecular Catalysis A: Chemical, Vol. 213, Issue 1 https://doi.org/10.1016/j.molcata.2003.10.049	journal	April 2004
Catalyst Inefficiencies: Supported Ring-Opening Metathesis Polymerization Catalyst Yields Its Ensemble Rate from a Small Number of Molecular Active Sites Easter, Quinn T.; Trauschke, Vanessa; Blum, Suzanne A. ACS Catalysis, Vol. 5, Issue 4 https://doi.org/10.1021/acscatal.5b00046	journal	March 2015
Structure–Reactivity Studies of Intermediates for Mechanistic Information by Subensemble Fluorescence Microscopy Kitagawa, Kazuhiro; Blum, Suzanne A. ACS Catalysis, Vol. 7, Issue 6 https://doi.org/10.1021/acscatal.7b00627	journal	April 2017
Nanoscale Study of Polymer Dynamics Keshavarz, Masoumeh; Engelkamp, Hans; Xu, Jialiang ACS Nano, Vol. 10, Issue 1 https://doi.org/10.1021/acsnano.5b06931	journal	December 2015
Propene Polymerization with Silica-Supported Metallocene/MAO Catalysts Fink, Gerhard; Steinmetz, Bernd; Zechlin, Joachim Chemical Reviews, Vol. 100, Issue 4 https://doi.org/10.1021/cr9804689	journal	April 2000
Homogeneous Metathesis Polymerization by Well-Defined Group VI and Group VIII Transition-Metal Alkylidenes: Fundamentals and Applications in the Preparation of Advanced Materials Buchmeiser, Michael R. Chemical Reviews, Vol. 100, Issue 4 https://doi.org/10.1021/cr990248a	journal	April 2000
Homogeneous vs Heterogeneous Polymerization Catalysis Revealed by Single-Particle Fluorescence Microscopy Esfandiari, N. Melody; Blum, Suzanne A. Journal of the American Chemical Society, Vol. 133, Issue 45 https://doi.org/10.1021/ja2085405	journal	November 2011
Phase Separation Polymerization of Dicyclopentadiene Characterized by In Operando Fluorescence Microscopy Hensle, Eva M.; Blum, Suzanne A. Journal of the American Chemical Society, Vol. 135, Issue 33 https://doi.org/10.1021/ja405283k	journal	August 2013
Living Alternating Ring-Opening Metathesis Polymerization Based on Single Monomer Additions Elling, Benjamin R.; Xia, Yan Journal of the American Chemical Society, Vol. 137, Issue 31 https://doi.org/10.1021/jacs.5b05497	journal	July 2015
Single-Molecule Investigation of Initiation Dynamics of an Organometallic Catalyst Ng, James D.; Upadhyay, Sunil P.; Marquard, Angela N. Journal of the American Chemical Society, Vol. 138, Issue 11 https://doi.org/10.1021/jacs.6b00357	journal	March 2016
Single-Molecule, Single-Particle Approaches for Exploring the Structure and Kinetics of Nanocatalysts Tachikawa, Takashi; Majima, Tetsuro Langmuir, Vol. 28, Issue 24 https://doi.org/10.1021/la300177h	journal	February 2012
A Kinetic Model To Explain the Zero-Order Release of Drugs from Ionic Polymeric Drug Conjugates: Application to AMPS−Triflusal-Derived Polymeric Drugs Gallardo, Alberto; Rodríguez, Gema; Aguilar, María Rosa Macromolecules, Vol. 36, Issue 23 https://doi.org/10.1021/ma034248v	journal	November 2003
Heterogeneities of individual catalyst particles in space and time as monitored by spectroscopy Buurmans, Inge L. C.; Weckhuysen, Bert M. Nature Chemistry, Vol. 4, Issue 11 https://doi.org/10.1038/nchem.1478	journal	October 2012
Opportunities and challenges in single-molecule and single-particle fluorescence microscopy for mechanistic studies of chemical reactions Cordes, Thorben; Blum, Suzanne A. Nature Chemistry, Vol. 5, Issue 12 https://doi.org/10.1038/nchem.1800	journal	November 2013
Polymers and single molecule fluorescence spectroscopy, what can we learn? Wöll, Dominik; Braeken, Els; Deres, Ania Chem. Soc. Rev., Vol. 38, Issue 2 https://doi.org/10.1039/B704319H	journal	January 2009
Spatiotemporal catalytic dynamics within single nanocatalysts revealed by single-molecule microscopy Chen, Peng; Zhou, Xiaochun; Andoy, Nesha May Chem. Soc. Rev., Vol. 43, Issue 4 https://doi.org/10.1039/C3CS60215J	journal	January 2014
Location change method for imaging chemical reactivity and catalysis with single-molecule and -particle fluorescence microscopy Blum, S. A. Physical Chemistry Chemical Physics, Vol. 16, Issue 31 https://doi.org/10.1039/C4CP00353E	journal	January 2014
Dye synthesis in the Pechmann reaction: catalytic behaviour of samarium oxide nanoparticles studied using single molecule fluorescence microscopy Hodgson, Gregory K.; Impellizzeri, Stefania; Scaiano, Juan C. Chemical Science, Vol. 7, Issue 2 https://doi.org/10.1039/C5SC03214H	journal	January 2016
A two-color fluorogenic carbene complex for tagging olefins via metathesis reaction Wirtz, Marcel; Grüter, Andreas; Heib, Florian Methods and Applications in Fluorescence, Vol. 3, Issue 4 https://doi.org/10.1088/2050-6120/3/4/044001	journal	September 2015
Single polymer growth dynamics Liu, Chunming; Kubo, Kaori; Wang, Endian Science, Vol. 358, Issue 6361 https://doi.org/10.1126/science.aan6837	journal	October 2017
Molecular diffusion in polymeric systems Duda, J. L. Pure and Applied Chemistry, Vol. 57, Issue 11 https://doi.org/10.1351/pac198557111681	journal	January 1985

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