Source:http://linkedlifedata.com/resource/pubmed/id/15303873
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rdf:type | |
lifeskim:mentions | |
pubmed:issue |
32
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pubmed:dateCreated |
2004-8-12
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pubmed:abstractText |
Kinetic studies of the reactions of cyclohexene silacyclopropane 1 and monosubstituted alkenes in the presence of 5 mol % of (Ph3P)2AgOTf suggested a possible mechanism for silver-mediated di-tert-butylsilylene transfer. The kinetic order in cyclohexene silacyclopropane 1 was determined to be one. Inverse kinetic saturation behavior (rate inhibition) was observed in monosubstituted alkene and cyclohexene concentrations. Saturation kinetic behavior in catalyst concentration was observed. A reactive intermediate, a silylsilver complex, was observed using low temperature 29Si NMR spectroscopy. Competition experiments between substituted styrenes and a deficient amount of 1 correlated well with the Hammett equation and provided a rho value of -0.62 +/- 0.02 using sigmap constants. These data support a mechanism involving reversible silver-promoted di-tert-butylsilylene extrusion from 1 followed by irreversible concerted electrophilic attack of the silylsilver intermediate on the alkene.
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pubmed:grant | |
pubmed:language |
eng
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pubmed:journal | |
pubmed:citationSubset |
IM
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pubmed:chemical |
http://linkedlifedata.com/resource/pubmed/chemical/Alkenes,
http://linkedlifedata.com/resource/pubmed/chemical/Cyclohexanes,
http://linkedlifedata.com/resource/pubmed/chemical/Cyclohexenes,
http://linkedlifedata.com/resource/pubmed/chemical/Cyclopropanes,
http://linkedlifedata.com/resource/pubmed/chemical/Silanes,
http://linkedlifedata.com/resource/pubmed/chemical/Silver,
http://linkedlifedata.com/resource/pubmed/chemical/cyclohexene
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pubmed:status |
MEDLINE
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pubmed:month |
Aug
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pubmed:issn |
0002-7863
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pubmed:author | |
pubmed:issnType |
Print
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pubmed:day |
18
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pubmed:volume |
126
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pubmed:owner |
NLM
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pubmed:authorsComplete |
Y
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pubmed:pagination |
9993-10002
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pubmed:dateRevised |
2007-11-14
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pubmed:meshHeading |
pubmed-meshheading:15303873-Alkenes,
pubmed-meshheading:15303873-Catalysis,
pubmed-meshheading:15303873-Cyclohexanes,
pubmed-meshheading:15303873-Cyclohexenes,
pubmed-meshheading:15303873-Cyclopropanes,
pubmed-meshheading:15303873-Kinetics,
pubmed-meshheading:15303873-Silanes,
pubmed-meshheading:15303873-Silver,
pubmed-meshheading:15303873-Thermodynamics
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pubmed:year |
2004
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pubmed:articleTitle |
Mechanism of silver-mediated di-tert-butylsilylene transfer from a silacyclopropane to an alkene.
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pubmed:affiliation |
Department of Chemistry, University of California, Irvine, California 92697-2025, USA.
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pubmed:publicationType |
Journal Article,
Research Support, U.S. Gov't, P.H.S.,
Research Support, Non-U.S. Gov't
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