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: 2023-08-05

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: http://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