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Mechanistic insights on platinum- and palladium-pincer catalyzed coupling and cyclopropanation reactions between olefins

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Title Mechanistic insights on platinum- and palladium-pincer catalyzed coupling and cyclopropanation reactions between olefins
 
Creator RAJEEV, R
SUNOJ, RB
 
Subject C-H ACTIVATION
INTERNAL OLEFINS
COMPLEXES
DENSITY
ETHYLENE
EXCHANGE
HYDROVINYLATION
THERMOCHEMISTRY
DEHYDROGENATION
HYDROGENATION
 
Description The mechanism of M(II)-PNP-pincer catalyzed reaction between (i) ethene, (ii) trans-butene with 2-methylbut-2-ene, 2,3-dimethylbut-2-ene and tert-butylbutene is examined by using density functional theory methods (where M = Pt or Pd). All key intermediates and transition states involved in the reaction are precisely located on the respective potential energy surfaces using the popular DFT functionals such as mPW1K, M06-2X, and B3LYP in conjunction with the 6-31+G** basis set. The reaction between these olefins can lead to a linear coupling product or a substituted cyclopropane. The energetic comparison between coupling as well as cyclopropanation pathways involving four pairs of olefins for both platinum (1-4) and palladium (5-8) catalyzed reactions is performed. The key events in the lower energy pathway in the mechanistic course involves (i) a C-C bond formation between the metal bound olefin (ethene or trans-butene) and a free olefin, and (ii) two successive [1,2] hydrogen migrations in the ensuing carbocationic intermediates (1c-4c, and 1d-4d), toward the formation of the coupling product. The computed barriers for these steps in the reaction of metal bound ethene to free tert-butylbutene (or other butenes) are found to be much lower than the corresponding steps when trans-butene is bound to the metal pincer. The Gibbs free energy differences between the transition states leading to the coupling product (TS(d-e)) and that responsible for cyclopropanated product (TS(d-g)) are found to be diminishingly closer in the case of the platinum pincer as compared to that in the palladium system. The computed energetics indicate that the coupled product prefers to remain as a metal olefin complex, consistent with the earlier experimental reports.
 
Publisher ROYAL SOC CHEMISTRY
 
Date 2014-10-15T12:23:22Z
2014-10-15T12:23:22Z
2012
 
Type Article
 
Identifier DALTON TRANSACTIONS, 41(27)8430-8440
http://dx.doi.org/10.1039/c2dt12325h
http://dspace.library.iitb.ac.in/jspui/handle/100/14895
 
Language en