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Theoretical study of the gas‐phase S N 2 reactions of X − with CH 3 OY (X, Y = Cl, Br, I)
Author(s) -
Gai JingGang,
Ren Yi
Publication year - 2006
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.21247
Subject(s) - chemistry , gas phase , oxygen atom , crystallography , oxygen , atom (system on chip) , bond length , molecule , crystal structure , organic chemistry , computer science , embedded system
The gas‐phase nucleophilic substitution reactions at saturated oxygen X − + CH 3 OY (X, Y = Cl, Br, I) have been investigated at the level of CCSD(T)/6‐311+G(2 df , p )//B3LYP/6‐311+G(2 df , p ). The calculated results indicate that X − preferably attacks oxygen atom of CH 3 OY via a S N 2 pathway. The central barriers and overall barriers are respectively in good agreement with both the predictions of Marcus equation and its modification, respectively. Central barrier heights (Δ H XY ≠and Δ H YX ≠ ) correlate well with the charges (Q) of the leaving groups (Y), Wiberg bond orders (BO) and the elongation of the bonds (OY and OX) in the transition structures. © 2007 Wiley Periodicals, Inc. Int J Quantum Chem, 2007