ACS Publications. Most Trusted. Most Cited. Most Read
Intermetallic Nanocatalysts from Heterobimetallic Group 10–14 Pyridine-2-thiolate Precursors
My Activity

Figure 1Loading Img
    Article

    Intermetallic Nanocatalysts from Heterobimetallic Group 10–14 Pyridine-2-thiolate Precursors
    Click to copy article linkArticle link copied!

    • Carena L. Daniels
      Carena L. Daniels
      Department of Chemistry, Iowa State University, Ames, Iowa 50011, United States
    • Megan Knobeloch
      Megan Knobeloch
      Department of Chemistry, Iowa State University, Ames, Iowa 50011, United States
    • Philip Yox
      Philip Yox
      Department of Chemistry, Iowa State University, Ames, Iowa 50011, United States
      More by Philip Yox
    • Marquix A. S. Adamson
      Marquix A. S. Adamson
      Department of Chemistry, Iowa State University, Ames, Iowa 50011, United States
    • Yunhua Chen
      Yunhua Chen
      Department of Chemistry, Iowa State University, Ames, Iowa 50011, United States
      More by Yunhua Chen
    • Rick W. Dorn
      Rick W. Dorn
      Department of Chemistry, Iowa State University, Ames, Iowa 50011, United States
      Ames Laboratory, Ames, Iowa 50011, United States
      More by Rick W. Dorn
    • Hao Wu
      Hao Wu
      School of Materials and Chemical Engineering, Ningbo University of Technology, Ningbo, Zhejiang, People’s Republic of China
      More by Hao Wu
    • Guoquan Zhou
      Guoquan Zhou
      School of Materials and Chemical Engineering, Ningbo University of Technology, Ningbo, Zhejiang, People’s Republic of China
      More by Guoquan Zhou
    • Huajun Fan
      Huajun Fan
      College of Chemical Engineering, Sichuan University of Science and Engineering, Zigong, Sichuan, People’s Republic of China
      More by Huajun Fan
    • Aaron J. Rossini
      Aaron J. Rossini
      Department of Chemistry, Iowa State University, Ames, Iowa 50011, United States
      Ames Laboratory, Ames, Iowa 50011, United States
    • Javier Vela*
      Javier Vela
      Department of Chemistry, Iowa State University, Ames, Iowa 50011, United States
      Ames Laboratory, Ames, Iowa 50011, United States
      *Email for J.V.: [email protected]
      More by Javier Vela
    Other Access OptionsSupporting Information (1)

    Organometallics

    Cite this: Organometallics 2020, 39, 7, 1092–1104
    Click to copy citationCitation copied!
    https://doi.org/10.1021/acs.organomet.9b00803
    Published March 3, 2020
    Copyright © 2020 American Chemical Society

    Abstract

    Click to copy section linkSection link copied!
    Abstract Image

    Intermetallic compounds are atomically ordered inorganic materials containing two or more transition metals and main-group elements in unique crystal structures. Intermetallics based on group 10 and group 14 metals have shown enhanced activity, selectivity, and durability in comparison to simple metals and alloys in many catalytic reactions. While high-temperature solid-state methods to prepare intermetallic compounds exist, softer synthetic methods can provide key advantages, such as enabling the preparation of metastable phases or of smaller particles with increased surface areas for catalysis. Here, we study a generalized family of heterobimetallic precursors to binary intermetallics, each containing a group 10 metal and a group 14 tetrel bonded together and supported by pincer-like pyridine-2-thiolate ligands. Upon thermal decomposition, these heterobimetallic complexes form 10–14 binary intermetallic nanocrystals. Experiments and density functional theory (DFT) computations help in better understanding the reactivity of these precursors toward the synthesis of specific intermetallic binary phases. Using Pd2Sn as an example, we demonstrate that nanoparticles made in this way can act as uniquely selective catalysts for the reduction of nitroarenes to azoxyarenes, which highlights the utility of the intermetallics made by our method. Employing heterobimetallic pincer complexes as precursors toward binary nanocrystals and other metal-rich intermetallics provides opportunities to explore the fundamental chemistry and applications of these materials.

    Copyright © 2020 American Chemical Society

    Read this article

    To access this article, please review the available access options below.

    Get instant access

    Purchase Access

    Read this article for 48 hours. Check out below using your ACS ID or as a guest.

    Recommended

    Access through Your Institution

    You may have access to this article through your institution.

    Your institution does not have access to this content. Add or change your institution or let them know you’d like them to include access.

    Supporting Information

    Click to copy section linkSection link copied!

    The Supporting Information is available free of charge at https://pubs.acs.org/doi/10.1021/acs.organomet.9b00803.

    • Computational data (frontier orbitals), crystallographic data, full thermal analysis and powder XRD measurements, particle size histogram for Pd2Sn, and solid-state (ss) NMR measurements for Cl2Sn(μ-PyS)2PdP(OPh)3 (5) and Pd2Sn (PDF)

    Accession Codes

    CCDC 19680371968040 contain the supplementary crystallographic data for this paper. These data can be obtained free of charge via www.ccdc.cam.ac.uk/data_request/cif, or by emailing [email protected], or by contacting The Cambridge Crystallographic Data Centre, 12 Union Road, Cambridge CB2 1EZ, UK; fax: +44 1223 336033.

    Terms & Conditions

    Most electronic Supporting Information files are available without a subscription to ACS Web Editions. Such files may be downloaded by article for research use (if there is a public use license linked to the relevant article, that license may permit other uses). Permission may be obtained from ACS for other uses through requests via the RightsLink permission system: http://pubs.acs.org/page/copyright/permissions.html.

    Cited By

    Click to copy section linkSection link copied!

    This article is cited by 12 publications.

    1. Matthew N. Gordon, Yanyao Liu, M. Kevin Brown, Sara E. Skrabalak. Single-Source Precursors for the Controlled Aqueous Synthesis of Bismuth Oxyhalides. Inorganic Chemistry 2023, 62 (24) , 9640-9648. https://doi.org/10.1021/acs.inorgchem.3c01114
    2. Carena L. Daniels, Eunbyeol Gi, Benjamin A. Atterberry, Rafael Blome-Fernández, Aaron J. Rossini, Javier Vela. Phosphine Ligand Binding and Catalytic Activity of Group 10–14 Heterobimetallic Complexes. Inorganic Chemistry 2022, 61 (18) , 6888-6897. https://doi.org/10.1021/acs.inorgchem.2c00229
    3. Carena L. Daniels, Da-Jiang Liu, Marquix A. S. Adamson, Megan Knobeloch, Javier Vela. Azo(xy) vs Aniline Selectivity in Catalytic Nitroarene Reduction by Intermetallics: Experiments and Simulations. The Journal of Physical Chemistry C 2021, 125 (44) , 24440-24450. https://doi.org/10.1021/acs.jpcc.1c08569
    4. Kristian L. Mears, Cary R. Stennett, Elina K. Taskinen, Caroline E. Knapp, Claire J. Carmalt, Heikki M. Tuononen, Philip P. Power. Molecular Complexes Featuring Unsupported Dispersion-Enhanced Aluminum–Copper and Gallium–Copper Bonds. Journal of the American Chemical Society 2020, 142 (47) , 19874-19878. https://doi.org/10.1021/jacs.0c10099
    5. Erik Wächtler, Robert Gericke, Theresa Block, Rainer Pöttgen, Jörg Wagler. Trivalent Antimony as L-, X-, and Z-Type Ligand: The Full Set of Possible Coordination Modes in Pt–Sb Bonds. Inorganic Chemistry 2020, 59 (20) , 15541-15552. https://doi.org/10.1021/acs.inorgchem.0c02615
    6. Álvaro García-Romero, Alex J. Plajer, Daniel Miguel, Dominic S. Wright, Andrew D. Bond, Celedonio M. Álvarez, Raúl García-Rodríguez. Tris(2-pyridyl) Bismuthines: Coordination Chemistry, Reactivity, and Anion-Triggered Pyridyl Coupling. Inorganic Chemistry 2020, 59 (10) , 7103-7116. https://doi.org/10.1021/acs.inorgchem.0c00579
    7. Marquix A. S. Adamson, Lin Wei, Philip Yox, Fatema H. B. Hafiz, Javier Vela. Nitrate and nitroarene hydrogenations catalyzed by alkaline-earth nickel phosphide clathrates. Dalton Transactions 2024, 53 (12) , 5702-5710. https://doi.org/10.1039/D4DT00332B
    8. Ratul Paul, Ankita Boruah, Risov Das, Subhajit Chakraborty, Kapil Chahal, Dhruba Jyoti Deka, Sebastian C. Peter, Binh Khanh Mai, John Mondal. Pyrolysis Free Out‐of‐Plane Co‐Single Atomic Sites in Porous Organic Photopolymer Stimulates Solar‐Powered CO 2 Fixation. Small 2024, 20 (11) https://doi.org/10.1002/smll.202305307
    9. Vincent Dardun, Tania Pinto, Loïc Benaillon, Laurent Veyre, Jules Galipaud, Clément Camp, Valérie Meille, Chloé Thieuleux. Easy preparation of small crystalline Pd 2 Sn nanoparticles in solution at room temperature. Dalton Transactions 2023, 52 (7) , 2157-2163. https://doi.org/10.1039/D2DT03476J
    10. R. Malcolm Charles, Timothy P. Brewster. H2 and carbon-heteroatom bond activation mediated by polarized heterobimetallic complexes. Coordination Chemistry Reviews 2021, 433 , 213765. https://doi.org/10.1016/j.ccr.2020.213765
    11. Wiktor Zierkiewicz, Mariusz Michalczyk, Steve Scheiner. Noncovalent Bonds through Sigma and Pi-Hole Located on the Same Molecule. Guiding Principles and Comparisons. Molecules 2021, 26 (6) , 1740. https://doi.org/10.3390/molecules26061740
    12. Erik Wächtler, Robert Gericke, Theresa Block, Birgit Gerke, Rainer Pöttgen, Jörg Wagler. Compounds of the types Pn (pyS) 3 ( Pn = P, As, Bi; pyS: pyridine-2-thiolate) and Sb(pyS) x Ph 3– x ( x = 3–1); molecular structures and electronic situations of the Pn atoms. Zeitschrift für Naturforschung B 2021, 76 (2) , 103-118. https://doi.org/10.1515/znb-2020-0171

    Organometallics

    Cite this: Organometallics 2020, 39, 7, 1092–1104
    Click to copy citationCitation copied!
    https://doi.org/10.1021/acs.organomet.9b00803
    Published March 3, 2020
    Copyright © 2020 American Chemical Society

    Article Views

    1319

    Altmetric

    -

    Citations

    Learn about these metrics

    Article Views are the COUNTER-compliant sum of full text article downloads since November 2008 (both PDF and HTML) across all institutions and individuals. These metrics are regularly updated to reflect usage leading up to the last few days.

    Citations are the number of other articles citing this article, calculated by Crossref and updated daily. Find more information about Crossref citation counts.

    The Altmetric Attention Score is a quantitative measure of the attention that a research article has received online. Clicking on the donut icon will load a page at altmetric.com with additional details about the score and the social media presence for the given article. Find more information on the Altmetric Attention Score and how the score is calculated.