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Computational Insight into a Gold(I) N-Heterocyclic Carbene Mediated Alkyne Hydroamination Reaction

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Title Computational Insight into a Gold(I) N-Heterocyclic Carbene Mediated Alkyne Hydroamination Reaction
 
Creator KATARI, M
RAO, MN
RAJARAMAN, G
GHOSH, P
 
Subject RING-OPENING POLYMERIZATION
POLARIZABLE CONTINUUM MODEL
MIXED AQUEOUS-MEDIUM
INTERMOLECULAR HYDROAMINATION
INTRAMOLECULAR HYDROAMINATION
TERMINAL ALKYNES
BASIS-SETS
MARKOVNIKOV HYDROAMINATION
THEORETICAL CHEMISTRY
CATALYTIC ACTION
 
Description A gold(I) N-heterocyclic carbene (NHC) complex mediated hydroamination of an alkyne has been modeled using density functional theory (DFT) study. In this regard, alkyne and amine coordination pathways have been investigated for the hydroamination reaction between two representative substrates, namely, MeC CH and PhNH2, catalyzed by a gold(I) NHC based (NHC)AuCl-type pre-catalyst, namely, [1,3-dimethylimidazol-2-ylidene]gold chloride. The amine coordination pathway displayed a lower activation barrier than the alkyne coordination pathway. The catalytic cycle is proposed to proceed via a crucial proton-transfer step occurring between the intermediates [(NHC)AuCH=CMeNH2Ph](+) (D) and [(NHC)Au(PhNHMeC=CH2)](+) (E), the activation barrier of which was found to be significantly reduced by a proton relay mechanism process assisted by the presence of any adventitious H2O molecule or even by any of the reacting PhNH2 substrates. The final hydroaminated enamine product, PhNHMeC=CH2, was further seen to be stabilized in its tautomeric imine form PhN=CMe2.
 
Publisher AMER CHEMICAL SOC
 
Date 2014-10-16T06:51:10Z
2014-10-16T06:51:10Z
2012
 
Type Article
 
Identifier INORGANIC CHEMISTRY, 51(10)5593-5604
http://dx.doi.org/10.1021/ic2024605
http://dspace.library.iitb.ac.in/jspui/handle/100/15479
 
Language en