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Titolo:
Pericyclic reactions of radical cations
Autore:
Saettel, NJ; Oxgaard, J; Wiest, O;
Indirizzi:
Univ Notre Dame, Dept Chem & Biochem, Notre Dame, IN 46556 USA Univ Notre Dame Notre Dame IN USA 46556 Biochem, Notre Dame, IN 46556 USA
Titolo Testata:
EUROPEAN JOURNAL OF ORGANIC CHEMISTRY
fascicolo: 8, , anno: 2001,
pagine: 1429 - 1439
SICI:
1434-193X(200104):8<1429:PRORC>2.0.ZU;2-A
Fonte:
ISI
Lingua:
ENG
Soggetto:
DIELS-ALDER REACTION; PHOTOINDUCED ELECTRON-TRANSFER; POTENTIAL-ENERGY SURFACE; RING-OPENING REACTION; AB-INITIO CALCULATIONS; VINYLCYCLOPROPANE-CYCLOPENTENE REARRANGEMENT; THERMAL UNIMOLECULAR VINYLCYCLOPROPANE; ACCEPTOR-SUBSTITUTED ENAMINES; TRANSFER CATALYZED-REACTIONS; THEORETICAL REACTION PATHS;
Keywords:
computational chemistry; density functional theory; electron transfer induced reactions; hydrocarbons; radical cations;
Tipo documento:
Review
Natura:
Periodico
Settore Disciplinare:
Physical, Chemical & Earth Sciences
Citazioni:
196
Recensione:
Indirizzi per estratti:
Indirizzo: Wiest, O Univ Notre Dame, Dept Chem & Biochem, Notre Dame, IN 46556 USA Univ Notre Dame Notre Dame IN USA 46556 Notre Dame, IN 46556 USA
Citazione:
N.J. Saettel et al., "Pericyclic reactions of radical cations", EUR J ORG C, (8), 2001, pp. 1429-1439

Abstract

Electron transfer catalysis is an efficient method for the catalysis of symmetry-forbidden or slow pericyclic reactions. Accurate quantum mechanical calculations are an important tool for gaining insights into the mechanistic details of these fast reactions involving radical cations. The current "state of the art" of computational studies of pericyclic reactions of radical cations is reviewed. In particular, four parent reaction types are discussed: (i) the ring-opening of the cyclobutane radical cation; (ii) the [2+2]cycloreversion of the cyclobutane radical cation; (iii) the radical cationDiels-Alder reaction of 1,3-butadiene and ethylene; and (iv) the [1,3] methylene shift in the vinylcyclopropane radical cation. The transfer of thesefindings to chemically more relevant substituted systems is also briefly discussed. The potential energy hypersurfaces obtained are very flat and have activation barriers that are significantly lower than the ones for the corresponding neutral reactions, which is in agreement with the large rate acceleration observed experimentally. Many of the located radical cation structures closely resemble their biradical counterparts in the neutral, stepwise pathways. The reactions generally follow a lower symmetry pathway, due to Jahn-Teller distortions induced by the unpaired electron. Finally, the results from computationally efficient B3LYP/6-31G* calculations are found tobe in good agreement with those from highly correlated MO calculations.

ASDD Area Sistemi Dipartimentali e Documentali, Università di Bologna, Catalogo delle riviste ed altri periodici
Documento generato il 24/09/20 alle ore 00:19:52