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Theoretical Study on the Mechanism of the Cycloaddition Reaction between Dichloromethylene Germylene and Ethylene
Author(s) -
Lu XiuHui,
Xu YueHua,
Yu HaiBin,
Lin Huang
Publication year - 2005
Publication title -
chinese journal of chemistry
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 1.28
H-Index - 41
eISSN - 1614-7065
pISSN - 1001-604X
DOI - 10.1002/cjoc.200591339
Subject(s) - chemistry , cycloaddition , exothermic reaction , singlet state , potential energy surface , ethylene , reaction mechanism , computational chemistry , photochemistry , transition state , activation barrier , ring (chemistry) , density functional theory , catalysis , molecule , organic chemistry , atomic physics , excited state , physics
Abstract The mechanism of a cycloaddition reaction between singlet dichloromethylene germylene and ethylene has been investigated with B3LYP/6‐31G* method, including geometry optimization and vibrational analysis for the involved stationary points on the potential energy surface. Energies for the involved conformations were calculated by CCSD(T)//B3LYP/6‐31G* method. On the basis of the surface energy profile obtained with CCSD(T)// B3LYP/6‐31G* method for the cycloaddition reaction between singlet dichloromethylene germylene and ethylene, it can be predicted that the dominant reaction pathway is that an intermediate INT1 is firstly formed between the two reactants through a barrier‐free exothermic reaction of 61.7 kJ/mol, and the intermediate INT1 then isomerizes to an active four‐membered ring product P2.1 via a transition state TS2 , an intermediate INT2 and a transition state TS2.1 , in which energy barriers are 57.7 and 42.2 kJ/mol, respectively.