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The Insertion of Singlet Silylene into Ethylene
Author(s) -
Anwari Freidun,
Gordon Mark S.
Publication year - 1983
Publication title -
israel journal of chemistry
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 0.908
H-Index - 54
eISSN - 1869-5868
pISSN - 0021-2148
DOI - 10.1002/ijch.198300018
Subject(s) - silylene , chemistry , singlet state , electronic correlation , ethylene , symmetry (geometry) , ab initio , valence (chemistry) , gaussian orbital , computational chemistry , molecular physics , atomic physics , silicon , molecule , physics , catalysis , organic chemistry , excited state , biochemistry , geometry , mathematics
Ab initio calculations at the minimal, split valence and extended basis set levels, both with and without electron correlation corrections, were used to study the insertion of singlet silylene into ethylene to form silacyclopropane. The least motion C 2v path is symmetry forbidden and an artificial barrier of about 36 kcal/mol is found within C 2v symmetry. Relaxation of symmetry to C, eliminates the symmetry forbiddenness of the reaction. The 3‐21G and 6‐31G* SCF calculations still predict a small barrier along this symmetry allowed path; however, the addition of second order correlation corrections results in the prediction of an insertion process with no barrier. The overall Δ E for the reaction is predicted by MP2/6‐31G*//3‐21G to be 47.9 kcal/mol.