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Reaction mechanism of palladium‐catalyzed silastannation of allenes by density functional theory
Author(s) -
Wang Meiyan,
Cheng Lin,
Hong Bo,
Wu Zhijian
Publication year - 2008
Publication title -
journal of computational chemistry
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 0.907
H-Index - 188
eISSN - 1096-987X
pISSN - 0192-8651
DOI - 10.1002/jcc.21176
Subject(s) - allene , chemistry , insertion reaction , density functional theory , mechanism (biology) , catalysis , palladium , stereochemistry , computational chemistry , organic chemistry , physics , quantum mechanics
The reaction mechanism of Pd(0)‐catalyzed allenes silastannation reaction is investigated by the density functional method B3LYP. The overall reaction mechanism is examined. For the allene insertion step, the PdSi bond is preferred over the PdSn bond. The electronic mechanism of the allene insertion into PdSi bond to form σ‐vinylpalladium (terminal‐insertion) and σ‐allylpalladium (internal‐insertion) insertion products is discussed in terms of the electron donation and back‐donation. It is found that the electron back‐donation is significant for both terminal‐ and internal‐insertion. During allene insertion into PdSi bond, internal‐insertion is preferred over terminal‐insertion. By using methylallene, the regio‐selectivity for the monosubstituted allene insertion into PdSi and PdSn bond is analyzed. © 2008 Wiley Periodicals, Inc. J Comput Chem 2009