Ring inversion in 1,4,7 cyclononatriene and analogues: Ab initio and DFT calculations and topological analysis
The multidimensional conformational potential energy hypersurfaces (PEHSs) for cis-cis-cis 1,4,7 cyclononatriene (I), Tribenzocyclononatriene (TBCN) (II), and cis-cis-cis cyclic triglycine (III) were comprehensively investigated at the Hartree-Fock (HF/6-31G(d)) and density functional theory (B3LYP/...
| Authors: | , , |
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| Format: | article |
| Status: | Published version |
| Publication Date: | 2008 |
| Country: | Argentina |
| Institution: | Consejo Nacional de Investigaciones Científicas y Técnicas |
| Repository: | CONICET Digital (CONICET) |
| Language: | English |
| OAI Identifier: | oai:ri.conicet.gov.ar:11336/147221 |
| Online Access: | http://hdl.handle.net/11336/147221 |
| Access Level: | Open access |
| Keyword: | AB INITIO CYCLIC-TRYGLICINE CYCLONONATRIENE DFT CALCULATIONS RING INVERSION TRIBENZOCYCLONONATRIENE https://purl.org/becyt/ford/1.4 https://purl.org/becyt/ford/1 |
| Summary: | The multidimensional conformational potential energy hypersurfaces (PEHSs) for cis-cis-cis 1,4,7 cyclononatriene (I), Tribenzocyclononatriene (TBCN) (II), and cis-cis-cis cyclic triglycine (III) were comprehensively investigated at the Hartree-Fock (HF/6-31G(d)) and density functional theory (B3LYP/6-31G(d,p)) levels of theory. The equilibrium structures, their relative stability, and the transition state (TS) structures involved in the conformational interconversion pathways were analyzed. Altogether, four geometries (two low-energy conformations and two transition states) were found to be important for a description of the conformational features of compounds I-III. B3LYP/aug-cc-pvdz//B31YP/6-31G(d,p) and MP2/6-31G(d,p)//B3LYP/6-31G(d,p) single point calculations predict that the conformational interconversion between crown and twist forms requires 14.01, 26.71, and 17.79 kcal/mol for compounds I, II, and III, respectively, which is in agreement with the available experimental data. A topological study of the conformational PEHSs of compounds I-III was performed. Our results allow us to form a concise idea about the internal intricacies of the PEHSs of compounds I-III, describing the conformations as well as the conformational interconversion process in these hypersurfaces. |
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