Ring Inversion in 1,4,7 Cyclononatriene and Analogues. Ab initio and DFT calculations and Topological Analysis

M.A.ZAMORA, F.SUVIRE R.D.ENRIZ

JOURNAL OF COMPUTATIONAL CHEMISTRY

Wiley

Año: 2008 vol. 29 p. 280 - 290

0192-8651

Abstract: 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//B3lYP/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. interconversion process in these hypersurfaces. about the internal intricacies of the PEHSs of compounds I–III, describing the conformations as well as the conformational interconversion process in these hypersurfaces. interconversion process in these hypersurfaces. 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. interconversion process in these hypersurfaces. about the internal intricacies of the PEHSs of compounds I–III, describing the conformations as well as the conformational interconversion process in these hypersurfaces. interconversion process in these hypersurfaces. B3LYP/aug-cc-pvdz//B3lYP/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. interconversion process in these hypersurfaces. about the internal intricacies of the PEHSs of compounds I–III, describing the conformations as well as the conformational interconversion process in these hypersurfaces. interconversion process in these hypersurfaces. 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. interconversion process in these hypersurfaces. about the internal intricacies of the PEHSs of compounds I–III, describing the conformations as well as the conformational interconversion process in these hypersurfaces. interconversion process in these hypersurfaces. 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//B3lYP/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. interconversion process in these hypersurfaces. about the internal intricacies of the PEHSs of compounds I–III, describing the conformations as well as the conformational interconversion process in these hypersurfaces. interconversion process in these hypersurfaces. 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. interconversion process in these hypersurfaces. about the internal intricacies of the PEHSs of compounds I–III, describing the conformations as well as the conformational interconversion process in these hypersurfaces. interconversion process in these hypersurfaces. B3LYP/aug-cc-pvdz//B3lYP/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. interconversion process in these hypersurfaces. about the internal intricacies of the PEHSs of compounds I–III, describing the conformations as well as the conformational interconversion process in these hypersurfaces. interconversion process in these hypersurfaces. 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. interconversion process in these hypersurfaces. about the internal intricacies of the PEHSs of compounds I–III, describing the conformations as well as the conformational interconversion process in these hypersurfaces. interconversion process in these hypersurfaces. (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//B3lYP/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. interconversion process in these hypersurfaces. about the internal intricacies of the PEHSs of compounds I–III, describing the conformations as well as the conformational interconversion process in these hypersurfaces. interconversion process in these hypersurfaces. 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. interconversion process in these hypersurfaces. about the internal intricacies of the PEHSs of compounds I–III, describing the conformations as well as the conformational interconversion process in these hypersurfaces. interconversion process in these hypersurfaces. B3LYP/aug-cc-pvdz//B3lYP/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. interconversion process in these hypersurfaces. about the internal intricacies of the PEHSs of compounds I–III, describing the conformations as well as the conformational interconversion process in these hypersurfaces. interconversion process in these hypersurfaces. 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. interconversion process in these hypersurfaces. about the internal intricacies of the PEHSs of compounds I–III, describing the conformations as well as the conformational interconversion process in these hypersurfaces. interconversion process in these hypersurfaces. 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//B3lYP/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. interconversion process in these hypersurfaces. about the internal intricacies of the PEHSs of compounds I–III, describing the conformations as well as the conformational interconversion process in these hypersurfaces. interconversion process in these hypersurfaces. 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. interconversion process in these hypersurfaces. about the internal intricacies of the PEHSs of compounds I–III, describing the conformations as well as the conformational interconversion process in these hypersurfaces. interconversion process in these hypersurfaces. B3LYP/aug-cc-pvdz//B3lYP/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. interconversion process in these hypersurfaces. about the internal intricacies of the PEHSs of compounds I–III, describing the conformations as well as the conformational interconversion process in these hypersurfaces. interconversion process in these hypersurfaces. 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. interconversion process in these hypersurfaces. about the internal intricacies of the PEHSs of compounds I–III, describing the conformations as well as the conformational interconversion process in these hypersurfaces. interconversion process in these hypersurfaces. 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//B3lYP/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. interconversion process in these hypersurfaces. about the internal intricacies of the PEHSs of compounds I–III, describing the conformations as well as the conformational interconversion process in these hypersurfaces. interconversion process in these hypersurfaces. 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. interconversion process in these hypersurfaces. about the internal intricacies of the PEHSs of compounds I–III, describing the conformations as well as the conformational interconversion process in these hypersurfaces. interconversion process in these hypersurfaces. B3LYP/aug-cc-pvdz//B3lYP/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. interconversion process in these hypersurfaces. about the internal intricacies of the PEHSs of compounds I–III, describing the conformations as well as the conformational interconversion process in these hypersurfaces. interconversion process in these hypersurfaces. 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. interconversion process in these hypersurfaces. about the internal intricacies of the PEHSs of compounds I–III, describing the conformations as well as the conformational interconversion process in these hypersurfaces. interconversion process in these hypersurfaces. 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//B3lYP/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. interconversion process in these hypersurfaces. about the internal intricacies of the PEHSs of compounds I–III, describing the conformations as well as the conformational interconversion process in these hypersurfaces. interconversion process in these hypersurfaces. 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. interconversion process in these hypersurfaces. about the internal intricacies of the PEHSs of compounds I–III, describing the conformations as well as the conformational interconversion process in these hypersurfaces. interconversion process in these hypersurfaces. B3LYP/aug-cc-pvdz//B3lYP/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. interconversion process in these hypersurfaces. about the internal intricacies of the PEHSs of compounds I–III, describing the conformations as well as the conformational interconversion process in these hypersurfaces. interconversion process in these hypersurfaces. 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. interconversion process in these hypersurfaces. about the internal intricacies of the PEHSs of compounds I–III, describing the conformations as well as the conformational interconversion process in these hypersurfaces. interconversion process in these hypersurfaces. 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//B3lYP/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. interconversion process in these hypersurfaces. about the internal intricacies of the PEHSs of compounds I–III, describing the conformations as well as the conformational interconversion process in these hypersurfaces. interconversion process in these hypersurfaces. 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. interconversion process in these hypersurfaces. about the internal intricacies of the PEHSs of compounds I–III, describing the conformations as well as the conformational interconversion process in these hypersurfaces. interconversion process in these hypersurfaces. B3LYP/aug-cc-pvdz//B3lYP/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. interconversion process in these hypersurfaces. about the internal intricacies of the PEHSs of compounds I–III, describing the conformations as well as the conformational interconversion process in these hypersurfaces. interconversion process in these hypersurfaces. 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. interconversion process in these hypersurfaces. about the internal intricacies of the PEHSs of compounds I–III, describing the conformations as well as the conformational interconversion process in these hypersurfaces. interconversion process in these hypersurfaces. I–III. B3LYP/aug-cc-pvdz//B3lYP/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. interconversion process in these hypersurfaces. about the internal intricacies of the PEHSs of compounds I–III, describing the conformations as well as the conformational interconversion process in these hypersurfaces. interconversion process in these hypersurfaces. 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. interconversion process in these hypersurfaces. about the internal intricacies of the PEHSs of compounds I–III, describing the conformations as well as the conformational interconversion process in these hypersurfaces. interconversion process in these hypersurfaces. 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. interconversion process in these hypersurfaces. about the internal intricacies of the PEHSs of compounds I–III, describing the conformations as well as the conformational interconversion process in these hypersurfaces. interconversion process in these hypersurfaces. 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. interconversion process in these hypersurfaces. I–III, describing the conformations as well as the conformational interconversion process in these hypersurfaces.