ACS Publications. Most Trusted. Most Cited. Most Read
Gas-Phase Ion Chemistry of Metalloporphyrin Anions with Molecular Oxygen: Probing the Influence of the Oxidation and Spin State of the Central Transition Metal by Experiment and Theory

OR SEARCH CITATIONS

My Activity
Publications

Figure 1Loading Img
Download Hi-Res ImageDownload to MS-PowerPointCite This:J. Phys. Chem. A 2018, 122, 17, 4357-4365
    Article

    Gas-Phase Ion Chemistry of Metalloporphyrin Anions with Molecular Oxygen: Probing the Influence of the Oxidation and Spin State of the Central Transition Metal by Experiment and Theory
    Click to copy article linkArticle link copied!

    • Tatjana Archipov
      Tatjana Archipov
      Institut für Physikalische Chemie and Institut für Nanotechnologie, Karlsruhe Institute of Technology, Kaiserstrasse 12, 76128 Karlsruhe, Germany
      More by Tatjana Archipov
    • Justin K. Kirkland
      Justin K. Kirkland
      Department of Chemistry, University of Tennessee, Knoxville, Tennessee 37996, United States
      More by Justin K. Kirkland
    • Konstantinos D. Vogiatzis
      Konstantinos D. Vogiatzis
      Institut für Physikalische Chemie and Institut für Nanotechnologie, Karlsruhe Institute of Technology, Kaiserstrasse 12, 76128 Karlsruhe, Germany
      Department of Chemistry, University of Tennessee, Knoxville, Tennessee 37996, United States
      More by Konstantinos D. Vogiatzis
    • Annika Steiner
      Annika Steiner
      Fachbereich Chemie and Forschungszentrum OPTIMAS, Technische Universität Kaiserslautern, 67663 Kaiserslautern, Germany
      More by Annika Steiner
    • Gereon Niedner-Schatteburg
      Gereon Niedner-Schatteburg
      Fachbereich Chemie and Forschungszentrum OPTIMAS, Technische Universität Kaiserslautern, 67663 Kaiserslautern, Germany
      More by Gereon Niedner-Schatteburg
      Orcidhttp://orcid.org/0000-0001-7240-6673
    • Patrick Weis
      Patrick Weis
      Institut für Physikalische Chemie and Institut für Nanotechnologie, Karlsruhe Institute of Technology, Kaiserstrasse 12, 76128 Karlsruhe, Germany
      More by Patrick Weis
      Orcidhttp://orcid.org/0000-0001-7006-6759
    • Karin Fink
      Karin Fink
      Institut für Physikalische Chemie and Institut für Nanotechnologie, Karlsruhe Institute of Technology, Kaiserstrasse 12, 76128 Karlsruhe, Germany
      More by Karin Fink
    • Oliver Hampe
      Oliver Hampe
      Institut für Physikalische Chemie and Institut für Nanotechnologie, Karlsruhe Institute of Technology, Kaiserstrasse 12, 76128 Karlsruhe, Germany
      More by Oliver Hampe
    • Manfred M. Kappes*
      Manfred M. Kappes
      Institut für Physikalische Chemie and Institut für Nanotechnologie, Karlsruhe Institute of Technology, Kaiserstrasse 12, 76128 Karlsruhe, Germany
      *E-mail: [email protected]
      More by Manfred M. Kappes
    Other Access OptionsSupporting Information (1)

    The Journal of Physical Chemistry A

    Cite this: J. Phys. Chem. A 2018, 122, 17, 4357–4365
    Click to copy citationCitation copied!
    https://doi.org/10.1021/acs.jpca.8b01715
    Published April 9, 2018
    Copyright © 2018 American Chemical Society
    Request reuse permissions

    Abstract

    Click to copy section linkSection link copied!
    Abstract Image

    We performed a comprehensive gas-phase experimental and quantum-chemical study of the binding properties of molecular oxygen to iron and manganese porphyrin anions. Temperature-dependent ion–molecule reaction kinetics as probed in a Fourier-transform ion-cyclotron resonance mass spectrometer reveal that molecular oxygen is bound by, respectively, 40.8 ± 1.4 and 67.4 ± 2.2 kJ mol–1 to the FeII or MnII centers of isolated tetra(4-sulfonatophenyl)metalloporphyrin tetraanions. In contrast, FeIII and MnIII trianion homologues were found to be much less reactive—indicating an upper bound to their dioxygen binding energies of 34 kJ mol–1. We modeled the corresponding O2 adsorbates at the density functional theory and CASPT2 levels. These quantum-chemical calculations verified the stronger O2 binding on the FeII or MnII centers and suggested that O2 binds as a superoxide anion.

    Copyright © 2018 American Chemical Society

    Subjects

    what are subjects

    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 on the ACS Publications website at DOI: 10.1021/acs.jpca.8b01715.

    • Schematic of T-Variable ICR Cell (90–420 K). Documentation of Cryogenic Pretrap Measurements (Kaiserslautern). DFT Geometries. Comparison between Complete 4-sulfonatophenyl and Hydrogen Substituted Models. Orbitals Included in the Active Space for the [M(P)]0/1+ and [M(P)(O2)]0/1+ Complexes. Relative Energy Differences for [M(P)]0/1+ and [M(P)(O2)]0/1+ Complexes. B3LYP Spin Densities for the [M-TPPS]3– Species. Orbitals Included in the Active Space for [Fe-TPPS]3–. Molecular Orbital Diagrams for [Fe(P)]0/1+ Complexes. Molecular Orbital Diagrams for [Fe(P)(O2)]0 and [Mn(P)(O2)]0 Complexes. Total energies, relative stabilities Δ of the 4–/3– complexes, and binding energies. M–O and O–O bond distances. Zero-point energies, enthalpies and entropies calculated with BP86. Vibrational frequencies for O2 bound systems, BP86 functional. Cartesian Coordinates of the [M(TPPS)]4–/3– and [M(TPPS)(O2)]4–/3– Complexes. Linear-logarithmic plot of the reaction kinetics of [MnIITPPS]4– with O2 (PDF)

    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 8 publications.

    1. Matías E. Regueiro Pschepiurca, Nahir Vadra, Sebastian A. Suarez. Versatile Metalloporphyrin‐Based Electrochemical Sensing Applications: From Small Gasotransmitters to Macromolecules. European Journal of Inorganic Chemistry 2023, 26 (17) https://doi.org/10.1002/ejic.202300005
    2. Niloufar Shafizadeh, Maria Elisa Crestoni, Aurélien de la Lande, Benoît Soep. Heme ligation in the gas phase. International Reviews in Physical Chemistry 2021, 40 (3) , 365-404. https://doi.org/10.1080/0144235X.2021.1952006
    3. Sebastian V. Kruppa, Cedric Groß, Xin Gui, Florian Bäppler, Björn Kwasigroch, Yu Sun, Rolf Diller, Wim Klopper, Gereon Niedner‐Schatteburg, Christoph Riehn, Werner R. Thiel. Photoinitiated Charge Transfer in a Triangular Silver(I) Hydride Complex and Its Oxophilicity. Chemistry – A European Journal 2019, 25 (48) , 11269-11284. https://doi.org/10.1002/chem.201901981
    4. Andrea Echeverri, Tatiana Gomez, C.Z. Hadad. Ammonia borane dehydrogenation tendencies using Pt4, Au4, and Pt2Au2 clusters as catalysts. Molecular Catalysis 2019, 471 , 9-20. https://doi.org/10.1016/j.mcat.2019.04.012
    5. Boutheïna Kerkeni, Adelia J. A. Aquino, Michael R. Berman, William L. Hase. Structures and binding energies for complexations of different spin states of Ni + and Ni 2+ to aromatic molecules. Molecular Physics 2019, 117 (9-12) , 1392-1403. https://doi.org/10.1080/00268976.2018.1552800
    6. Mohammad Aarabi, Reza Omidyan, Satchin Soorkia, Gilles Grégoire, Michel Broquier, Maria-Elisa Crestoni, Aurélien de la Lande, Benoît Soep, Niloufar Shafizadeh. The dramatic effect of N -methylimidazole on trans axial ligand binding to ferric heme: experiment and theory. Physical Chemistry Chemical Physics 2019, 21 (4) , 1750-1760. https://doi.org/10.1039/C8CP06210B
    7. Sebastian Dillinger, Gereon Niedner-Schatteburg. Cryo trapping by FT-MS for kinetics and spectroscopy. 2019, 593-621. https://doi.org/10.1016/B978-0-12-814013-0.00019-3
    8. Quan Manh Phung, Kristine Pierloot. The dioxygen adducts of iron and manganese porphyrins: electronic structure and binding energy. Physical Chemistry Chemical Physics 2018, 20 (25) , 17009-17019. https://doi.org/10.1039/C8CP03078B
    Download PDF
    Go to The Journal of Physical Chemistry A
    Get e-Alerts
    Get e-Alerts

    The Journal of Physical Chemistry A

    Cite this: J. Phys. Chem. A 2018, 122, 17, 4357–4365
    Click to copy citationCitation copied!
    https://doi.org/10.1021/acs.jpca.8b01715
    Published April 9, 2018
    Copyright © 2018 American Chemical Society
    Request reuse permissions

    Article Views

    998

    Altmetric

    -

    Citations

    8
    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.