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

  • Datos identificativos

    Identificador: imarina:9220639
    Autores:
    Garay-Ruiz DBo C
    Resumen:
    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.
  • Otros:

    Autor según el artículo: Garay-Ruiz D; Bo C
    Departamento: Química Física i Inorgànica
    Autor/es de la URV: Bo Jané, Carles
    Palabras clave: 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
    Resumen: 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.
    Áreas temáticas: 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
    Acceso a la licencia de uso: https://creativecommons.org/licenses/by/3.0/es/
    Direcció de correo del autor: carles.bo@urv.cat
    Identificador del autor: 0000-0001-9581-2922
    Fecha de alta del registro: 2024-07-27
    Volumen de revista: 27
    Versión del articulo depositado: info:eu-repo/semantics/publishedVersion
    Enlace a la fuente original: https://chemistry-europe.onlinelibrary.wiley.com/doi/10.1002/chem.202100755
    URL Documento de licencia: https://repositori.urv.cat/ca/proteccio-de-dades/
    Referencia al articulo segun fuente origial: Chemistry-A European Journal. 27 (45): 11618-11626
    Referencia de l'ítem segons les normes 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
    DOI del artículo: 10.1002/chem.202100755
    Entidad: Universitat Rovira i Virgili
    Año de publicación de la revista: 2021
    Tipo de publicación: Journal Publications
  • Palabras clave:

    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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