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Ab initio study of the mechanism of forming a spiro‐heterocyclic ring compound involving Si and Ge from dichlorosilylene germylidene(Cl 2 SiGe:) and formaldehyde
Author(s) -
Lu Xiuhui,
Lian Zhenxia,
Liu Dongting,
Bao Weijie
Publication year - 2012
Publication title -
international journal of quantum chemistry
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 0.484
H-Index - 105
eISSN - 1097-461X
pISSN - 0020-7608
DOI - 10.1002/qua.24361
Subject(s) - chemistry , ring (chemistry) , cycloaddition , formaldehyde , singlet state , ab initio , atom (system on chip) , computational chemistry , transition state , reaction mechanism , molecular orbital , crystallography , photochemistry , catalysis , molecule , organic chemistry , atomic physics , excited state , physics , computer science , embedded system
The mechanism of the cycloaddition reaction between singlet dichlorosilylene germylidene (Cl 2 SiGe:) and formaldehyde has been investigated with the CCSD(T)//MP2/6‐31G* method. From the potential energy profile, it could be predicted that the reaction has one dominant reaction pathway. The reaction rule presented is that the two reactants first form a four‐membered Si‐heterocyclic ring germylene through the [2 + 2] cycloaddition reaction. Because of the 4p unoccupied orbital of Ge atom in the four‐membered Si‐heterocyclic ring germylene and the π orbital of formaldehyde forming a π→p donor–acceptor bond, the four‐membered Si‐heterocyclic ring germylene further combines with formaldehyde to form an intermediate. Because the Ge atom in intermediate undergoes sp3 hybridization after transition state, then, the intermediate isomerizes to a spiro‐heterocyclic ring compound involving Si and Ge via a transition state. © 2012 Wiley Periodicals, Inc.