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Theoretical examination of substituent effects on the stabilization of a SnY (Y = Sb and Bi) multiple bond
Author(s) -
Hu YaHui,
Su MingDer
Publication year - 2004
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.20356
Subject(s) - electronegativity , chemistry , substituent , steric effects , isomerization , molecule , computational chemistry , aryl , crystallography , stereochemistry , organic chemistry , alkyl , catalysis
The potential energy surface for the unimolecular rearrangement XSnY → TS → SnYX (Y = Sb, Bi) was investigated using the B3LYP and QCISD methods. To explore electronic effects on the relative stability of XSnY and SnYX, the first‐row substituents (X = H, Li, BeH, BH 2 , CH 3 , NH 2 , OH, F) have been used. Our theoretical findings suggest that the doubly bonded SnYX species are always both kinetically and thermodynamically more stable than their corresponding triply bonded isomers, XSnY, regardless of the electronegativity of the substituent X. Nevertheless, our model calculations indicate that an aryl group can, if sufficiently bulky, stabilize triply bonded XSnY molecules with respect to both isomerization and polymerization. That is to say, it is not electronic but steric effects that play a dominant role in stabilizing both SnSb and SnBi triple bonds. © 2004 Wiley Periodicals, Inc. Int J Quantum Chem, 2005