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Rationalizing the Mechanism of Peroxyformate Decomposition: Computational Insights To Understand Solvent Influence

  • Identification data

    Identifier: imarina:9220639
    Authors:
    Garay-Ruiz DBo C
    Abstract:
    The heterolytic decomposition of tert-butyl peroxyformate to tert-butanol and carbon dioxide, catalyzed by pyridine, is a long-known example of a reaction whose kinetics are strongly affected by solvent polarity. From DFT and ab initio methods together with the SMD implicit solvation model, an extension on the formerly accepted mechanism is proposed. This novel proposal involves the formation of a carbonic acid ester intermediate and its further decomposition, through an unreported pyridine-mediated stepwise route. Computed barriers for this mechanism at DLPNO/CCSD(T)-def2-TZVP are in excellent agreement with experimental kinetic data across different solvents. Furthermore, the strong relationships between activation energies, geometric parameters in the transition state and the characteristics of the different solvents are also analyzed in depth.
  • Others:

    Author, as appears in the article.: Garay-Ruiz D; Bo C
    Department: Química Física i Inorgànica
    URV's Author/s: Bo Jané, Carles
    Keywords: Peroxides Organocatalysis Orbital coupled-cluster Implicit solvent Dft Carbonates solvation set peroxides organocatalysis implicit solvent free-energy epoxides dft cyclic carbonates complex co2 carbonic-acid ammonia
    Abstract: The heterolytic decomposition of tert-butyl peroxyformate to tert-butanol and carbon dioxide, catalyzed by pyridine, is a long-known example of a reaction whose kinetics are strongly affected by solvent polarity. From DFT and ab initio methods together with the SMD implicit solvation model, an extension on the formerly accepted mechanism is proposed. This novel proposal involves the formation of a carbonic acid ester intermediate and its further decomposition, through an unreported pyridine-mediated stepwise route. Computed barriers for this mechanism at DLPNO/CCSD(T)-def2-TZVP are in excellent agreement with experimental kinetic data across different solvents. Furthermore, the strong relationships between activation energies, geometric parameters in the transition state and the characteristics of the different solvents are also analyzed in depth.
    Thematic Areas: Química Organic chemistry Medicina i Materiais Interdisciplinar General medicine General chemistry Farmacia Engenharias iii Engenharias ii Ciências biológicas iii Ciências biológicas ii Ciências biológicas i Ciências agrárias i Chemistry, multidisciplinary Chemistry (miscellaneous) Chemistry (all) Chemistry Catalysis Biotecnología Biodiversidade Astronomia / física
    licence for use: https://creativecommons.org/licenses/by/3.0/es/
    Author's mail: carles.bo@urv.cat
    Author identifier: 0000-0001-9581-2922
    Record's date: 2024-07-27
    Journal volume: 27
    Papper version: info:eu-repo/semantics/publishedVersion
    Link to the original source: https://chemistry-europe.onlinelibrary.wiley.com/doi/10.1002/chem.202100755
    Licence document URL: https://repositori.urv.cat/ca/proteccio-de-dades/
    Papper original source: Chemistry-A European Journal. 27 (45): 11618-11626
    APA: Garay-Ruiz D; Bo C (2021). Rationalizing the Mechanism of Peroxyformate Decomposition: Computational Insights To Understand Solvent Influence. Chemistry-A European Journal, 27(45), 11618-11626. DOI: 10.1002/chem.202100755
    Article's DOI: 10.1002/chem.202100755
    Entity: Universitat Rovira i Virgili
    Journal publication year: 2021
    Publication Type: Journal Publications
  • Keywords:

    Catalysis,Chemistry,Chemistry (Miscellaneous),Chemistry, Multidisciplinary,Organic Chemistry
    Peroxides
    Organocatalysis
    Orbital coupled-cluster
    Implicit solvent
    Dft
    Carbonates
    solvation
    set
    peroxides
    organocatalysis
    implicit solvent
    free-energy
    epoxides
    dft
    cyclic carbonates
    complex
    co2
    carbonic-acid
    ammonia
    Química
    Organic chemistry
    Medicina i
    Materiais
    Interdisciplinar
    General medicine
    General chemistry
    Farmacia
    Engenharias iii
    Engenharias ii
    Ciências biológicas iii
    Ciências biológicas ii
    Ciências biológicas i
    Ciências agrárias i
    Chemistry, multidisciplinary
    Chemistry (miscellaneous)
    Chemistry (all)
    Chemistry
    Catalysis
    Biotecnología
    Biodiversidade
    Astronomia / física
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