DFT study on the cycloreversion of thietane radical cations
The molecular mechanism of the cycloreversion (CR) of thietane radical cations has been analyzed in detail at the UB3LYP/6-31G* level of theory. Results have shown that the process takes place via a stepwise mechanism leading to alkenes and thiobenzophenone; alternatively, formal [4 + 2] cycloadduct...
| Autores: | , , , |
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| Tipo de recurso: | artículo |
| Estado: | Versión publicada |
| Fecha de publicación: | 2011 |
| País: | Argentina |
| Institución: | Consejo Nacional de Investigaciones Científicas y Técnicas |
| Repositorio: | CONICET Digital (CONICET) |
| Idioma: | inglés |
| OAI Identifier: | oai:ri.conicet.gov.ar:11336/65854 |
| Acceso en línea: | http://hdl.handle.net/11336/65854 |
| Access Level: | acceso abierto |
| Palabra clave: | Radical Cation Ciclorevesion Dft Calculation Thietane https://purl.org/becyt/ford/1.4 https://purl.org/becyt/ford/1 |
| Sumario: | The molecular mechanism of the cycloreversion (CR) of thietane radical cations has been analyzed in detail at the UB3LYP/6-31G* level of theory. Results have shown that the process takes place via a stepwise mechanism leading to alkenes and thiobenzophenone; alternatively, formal [4 + 2] cycloadducts are obtained. Thus, the CR of radical cations 1a,b •+ is initiated by C2-C3 bond breaking, giving common intermediates INa,b. At this stage, two reaction pathways are feasible involving ion molecule complexes IMCa,b (i) or radical cations 4a,b •+ (ii). Calculations support that 1a •+ follows reaction pathway ii (leading to the formal [4 + 2] cycloadducts 5a). By contrast, 1b •+ follows pathway i, leading to trans-stilbene radical cation (2b •+) and thiobenzophenone. © 2011 American Chemical Society. |
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