Quantum study on the electrocyclic reactions of CH2CHCHCHX (XH, F, Cl)

• Published in: International journal of quantum chemistry Vol. 100; no. 3; pp. 288 - 292
• Main Authors: Deng, Ping, Li, Lai-Cai, Tian, An-Min, Wong, Ning-Bew
• Format: Journal Article
• Language: English
• Published: New York John Wiley & Sons, Inc 05.11.2004
• Subjects: 3-butadiene; cis-1; cis‐1,3‐butadiene; density functional theory; monohalogen-butadiene; transition states
• ISSN: 0020-7608; 1097-461X
• DOI: 10.1002/qua.20159

The microscopic mechanisms of the electrocyclic reactions for cis‐1,3‐butadiene and its monofluoro‐, monochloroderivatives have been studied by density functional theory (DFT), using the B3LYP method and 6‐311++G** basis sets. We optimized the geometric configurations of reactants, transition states, and products; verified all the probable transition states through vibrational analysis; and calculated the relative single‐point energies at the QCISD(T)/6‐311++G**//B3LYP/6‐311++G**. The results show that the monofluoro‐, monochloroderivatives of cis‐1,3‐butadiene both have two conformers; the reactant favors the electrocyclic reaction when one outboard hydrogen atom of the CH2 groups is substituted by the fluorine or chlorine atom. © 2004 Wiley Periodicals, Inc. Int J Quantum Chem, 2004