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