| Full text | |
| Author(s): |
Total Authors: 2
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| Affiliation: | [1] Univ Estadual Campinas, Inst Chem, Dept Organ Chem, BR-13083970 Campinas, SP - Brazil
Total Affiliations: 1
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| Document type: | Journal article |
| Source: | Physical Chemistry Chemical Physics; v. 22, n. 46, p. 27173-27177, DEC 14 2020. |
| Web of Science Citations: | 1 |
| Abstract | |
Steric, electrostatic and hyperconjugative effects were evaluated in the natural bond orbital framework as candidate sources of the preferred geometry of hydroperoxides. Stabilising 1,2-H delta+-O delta- electrostatic interactions and n(O) -> sigma{*}(OR) hyperconjugative interactions were found to be the driving force for the preferred anticlinal or perpendicular geometries, respectively. There is an interesting interplay between these two effects: when one increases, the other decreases. On the other hand, steric effects showed negligible contributions to the conformational behaviour of the studied molecules. Also, HO-OR bond dissociation energy appeared to be dependent on RO radical stability, which is governed by hyperconjugation. (AU) | |
| FAPESP's process: | 18/21979-9 - Physical organic chemistry studies of peroxides and dissulfides for the understanding of their properties and reactivities |
| Grantee: | Marco Aurélio de Souza Afonso |
| Support Opportunities: | Scholarships in Brazil - Scientific Initiation |
| FAPESP's process: | 18/03910-1 - Physicochemical studies of fluorinated organic compounds: experimental and theoretical approaches |
| Grantee: | Rodrigo Antonio Cormanich |
| Support Opportunities: | Research Grants - Young Investigators Grants |
| FAPESP's process: | 19/22099-5 - Mechanical investigations of the Mannich reaction using kinetic isotopic effects of 13C in natural abundance and theoretical calculations |
| Grantee: | Marco Aurélio de Souza Afonso |
| Support Opportunities: | Scholarships in Brazil - Doctorate (Direct) |