THEORETICAL STUDY OF THE MECHANISM OF CYCLOADDITION REACTION BETWEEN DICHLORO-SILYLENE CARBENE(CL2SI=C:) AND ACETONE

The mechanism of the cycloaddition reaction between singlet dichloro-silylene carbene and acetone has been investigated with DFT, including geometry optimization and vibrational analysis for the involved stationary points on the potential energy surface. The energies of the different conformations a...

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Autores principales:	LU,XIUHUI, XIANG,PINGPING, SHI,LEYI , HAN,JUNFENG, LIAN,ZHENXIA
Lenguaje:	English
Publicado:	Sociedad Chilena de Química 2010
Materias:	Dichloro-silylene carbene Cycloadditional reaction Potential energy surface
Acceso en línea:	http://www.scielo.cl/scielo.php?script=sci_arttext&pid=S0717-97072010000300014
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spelling	oai:scielo:S0717-970720100003000142011-01-25THEORETICAL STUDY OF THE MECHANISM OF CYCLOADDITION REACTION BETWEEN DICHLORO-SILYLENE CARBENE(CL2SI=C:) AND ACETONELU,XIUHUIXIANG,PINGPINGSHI,LEYI HAN,JUNFENGLIAN,ZHENXIA Dichloro-silylene carbene Cycloadditional reaction Potential energy surface The mechanism of the cycloaddition reaction between singlet dichloro-silylene carbene and acetone has been investigated with DFT, including geometry optimization and vibrational analysis for the involved stationary points on the potential energy surface. The energies of the different conformations are calculated by CCSD(T)//B3LYP/6-31G* method. From the potential energy profile, it can be predicted that the reaction has two competitive dominant reaction pathways. The channel (I) consists of two steps: (1) the two reactants firstly form a four-membered ring intermediate through a barrier-free exothermic reaction of 307.1 kJ/mol; (2) four-membered ring intermediate then isomerizes to a CH3-transfer product via a transition state with energy barrier of 11.3 kJ/mol. The process of channel (II) is as following: on the basis of four-membered ring intermediate created between the two reactants, four-membered ring intermediate further reacts with acetone to form the intermediate through a barrier-free exothermic reaction of 165.8 kJ/mol; Then, intermediate isomerizes to a silicic bis-heterocyclic product via a transition state, for which the barrier is 57.6 kJ/mol.info:eu-repo/semantics/openAccessSociedad Chilena de QuímicaJournal of the Chilean Chemical Society v.55 n.3 20102010-01-01text/htmlhttp://www.scielo.cl/scielo.php?script=sci_arttext&pid=S0717-97072010000300014en10.4067/S0717-97072010000300014
institution	Scielo Chile
collection	Scielo Chile
language	English
topic	Dichloro-silylene carbene Cycloadditional reaction Potential energy surface
spellingShingle	Dichloro-silylene carbene Cycloadditional reaction Potential energy surface LU,XIUHUI XIANG,PINGPING SHI,LEYI HAN,JUNFENG LIAN,ZHENXIA THEORETICAL STUDY OF THE MECHANISM OF CYCLOADDITION REACTION BETWEEN DICHLORO-SILYLENE CARBENE(CL2SI=C:) AND ACETONE
description	The mechanism of the cycloaddition reaction between singlet dichloro-silylene carbene and acetone has been investigated with DFT, including geometry optimization and vibrational analysis for the involved stationary points on the potential energy surface. The energies of the different conformations are calculated by CCSD(T)//B3LYP/6-31G* method. From the potential energy profile, it can be predicted that the reaction has two competitive dominant reaction pathways. The channel (I) consists of two steps: (1) the two reactants firstly form a four-membered ring intermediate through a barrier-free exothermic reaction of 307.1 kJ/mol; (2) four-membered ring intermediate then isomerizes to a CH3-transfer product via a transition state with energy barrier of 11.3 kJ/mol. The process of channel (II) is as following: on the basis of four-membered ring intermediate created between the two reactants, four-membered ring intermediate further reacts with acetone to form the intermediate through a barrier-free exothermic reaction of 165.8 kJ/mol; Then, intermediate isomerizes to a silicic bis-heterocyclic product via a transition state, for which the barrier is 57.6 kJ/mol.
author	LU,XIUHUI XIANG,PINGPING SHI,LEYI HAN,JUNFENG LIAN,ZHENXIA
author_facet	LU,XIUHUI XIANG,PINGPING SHI,LEYI HAN,JUNFENG LIAN,ZHENXIA
author_sort	LU,XIUHUI
title	THEORETICAL STUDY OF THE MECHANISM OF CYCLOADDITION REACTION BETWEEN DICHLORO-SILYLENE CARBENE(CL2SI=C:) AND ACETONE
title_short	THEORETICAL STUDY OF THE MECHANISM OF CYCLOADDITION REACTION BETWEEN DICHLORO-SILYLENE CARBENE(CL2SI=C:) AND ACETONE
title_full	THEORETICAL STUDY OF THE MECHANISM OF CYCLOADDITION REACTION BETWEEN DICHLORO-SILYLENE CARBENE(CL2SI=C:) AND ACETONE
title_fullStr	THEORETICAL STUDY OF THE MECHANISM OF CYCLOADDITION REACTION BETWEEN DICHLORO-SILYLENE CARBENE(CL2SI=C:) AND ACETONE
title_full_unstemmed	THEORETICAL STUDY OF THE MECHANISM OF CYCLOADDITION REACTION BETWEEN DICHLORO-SILYLENE CARBENE(CL2SI=C:) AND ACETONE
title_sort	theoretical study of the mechanism of cycloaddition reaction between dichloro-silylene carbene(cl2si=c:) and acetone
publisher	Sociedad Chilena de Química
publishDate	2010
url	http://www.scielo.cl/scielo.php?script=sci_arttext&pid=S0717-97072010000300014
work_keys_str_mv	AT luxiuhui theoreticalstudyofthemechanismofcycloadditionreactionbetweendichlorosilylenecarbenecl2sicandacetone AT xiangpingping theoreticalstudyofthemechanismofcycloadditionreactionbetweendichlorosilylenecarbenecl2sicandacetone AT shileyi theoreticalstudyofthemechanismofcycloadditionreactionbetweendichlorosilylenecarbenecl2sicandacetone AT hanjunfeng theoreticalstudyofthemechanismofcycloadditionreactionbetweendichlorosilylenecarbenecl2sicandacetone AT lianzhenxia theoreticalstudyofthemechanismofcycloadditionreactionbetweendichlorosilylenecarbenecl2sicandacetone
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THEORETICAL STUDY OF THE MECHANISM OF CYCLOADDITION REACTION BETWEEN DICHLORO-SILYLENE CARBENE(CL2SI=C:) AND ACETONE

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