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Mechanism of methylacetylene bisselenation catalyzed by palladium complex from density functional study
Author(s) -
Wang Meiyan,
Cheng Lin,
Wang Jinping,
Wu Zhijian
Publication year - 2010
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.21700
Subject(s) - palladium , regioselectivity , chemistry , migratory insertion , reductive elimination , insertion reaction , photochemistry , density functional theory , carbon monoxide , reaction mechanism , oxidative addition , catalysis , polymer chemistry , computational chemistry , organic chemistry
The reaction mechanism of Pd(0)‐catalyzed methylacetylene bisselenation reaction is investigated by using the density functional method. The overall reaction mechanism involves the oxidative addition, insertion, and reductive elimination steps. The regioselectivity has been investigated for the methylacetylene insertion into PdSe bond of both cis and trans palladium complexes. It is found that the methylacetylene insertion into PdSe bond of the trans palladium complex using the substituted carbon atom attached to selenyl group is preferred among the four pathways of methylacetylene insertion processes. The electronic mechanisms on the methylacetylene insertion into PdSe bond are discussed in terms of the Frontier molecular orbital interactions. In addition, the influence of carbon monoxide on methylacetylene bisselenation was studied and found that the methylacetylene coordination and insertion into PdSe bond take place first generating the PdC bond, followed by CO insertion into the PdC bond. © 2010 Wiley Periodicals, Inc. J Comput Chem, 2010.