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: 2023-08-05

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: http://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