title: Ab initio study on the mechanism of forming a germanic hetero-polycyclic compound between alkylidenegermylene and ethylene.
abstract: The mechanism of the cycloaddition reaction of forming a germanic hetero-polycyclic compound between singlet alkylidenegermylene and ethylene has been investigated with MP2/6-31G* method, including geometry optimization and vibrational analysis for the involved stationary points on the potential energy surface. The energies of the different conformations are calculated by CCSD(T)//MP2/6-31G* method. From the surface energy profile, it can be predicted that the dominant reaction pathway for this reaction consists of three steps: the two reactants first form a three-membered ring intermediate INT1 through a barrier-free exothermic reaction of 35.4 kJ/mol; this intermediate then isomerizes to an active four-membered ring product P2.1 via a transition-state TS2.1 with a barrier of 57.6 kJ/mol; finally, P2.1 further reacts with ethylene to form the germanic hetero-polycyclic compound P3, for which the barrier is only 0.8 kJ/mol. The rate of this reaction path considerably differs from other competitive reaction paths, indicating that the cycloaddition reaction has an excellent selectivity.
authors.affiliation: School of Chemistry and Chemical Engineering, Jinan University, Jinan, Shandong, 250022, People's Republic of China. lxh@ujn.edu.cn
authors.forename: Xiuhui
authors.initials: X
authors.lastname: Lu
authors.forename: Yuehua
authors.initials: Y
authors.lastname: Xu
authors.forename: Haibin
authors.initials: H
authors.lastname: Yu
authors.forename: Weirong
authors.initials: W
authors.lastname: Wu