Multistep conformational interconversion mechanism of cyclododecane. A simple and fast analysis using potential energy curves

EDGARDO J. SAAVEDRA; SEBASTIAN A. ANDUJAR; FERNANDO D. SUVIRE; MIGUEL A. ZAMORA; MONICA L. FREILE; RICARDO D. ENRIZ

INTERNATIONAL JOURNAL OF QUANTUM CHEMISTRY

JOHN WILEY & SONS INC

Año: 2011

0020-7608

An ab initio and Density Functional Theory (DFT) study of the conformational properties of cyclododecane was carried out. The energetically preferred equilibrium structures, their relative stability, and some of the transition state (TS) structures involved in the conformational interconversion pathways were analyzed from RHF/6-31G(d), B3LYP/6-31G(d,p) and B3LYP/6311++G(d,p) calculations. Aug-cc-pVDZ//B3LYP/6311++G(d,p) single point calculations predict that the multistep conformational interconversion mechanism requires 11.07 kcal/mol, which is in agreement with the available experimental data. These results allow us to form a concise idea about the internal intricacies of the preferred forms of cyclododecane, describing the conformations as well as the conformational interconversion processes in the conformational potential energy hypersurface. Our results indicated that performing an exhaustive analysis of the potential energy curves connecting the most representative conformations is a valid alternate tool to determine the principal conformational interconversion paths for cyclododecane. This methodology represents a satisfactory first approximation for the conformational analysis of medium- and large-size flexible cyclic compounds.