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Article: Reactions of stable silenes with Grignard reagents

TitleReactions of stable silenes with Grignard reagents
Authors
Issue Date1991
PublisherAmerican Chemical Society. The Journal's web site is located at http://pubs.acs.org/organometallics
Citation
Organometallics, 1991, v. 10 n. 9, p. 3292-3301 How to Cite?
AbstractGrignard reagents have been found to add to members of the family of stable silenes (Me3Si)RSi=C-(OSiMe3)R′ (R = Me3Si, Ph; R′ = Ad or t-Bu). Two types of product were formed, namely a family of compounds where one molecule of Grignard reagent R″MgX was involved, leading to products with the structures 6, Me3SiOSiRR″CHR′(SiMe3), and a family where two molecules of Grignard reagent were involved, leading to products with structures 7, RR″2SiCHR′(SiMe3). The crystal structure of one compound, 6baa (R = Ph, R′ = Ad, R″ = Me), was obtained, confirming the structure assigned to this family of compounds. It is evident that, in the course of forming these products, a trimethylsilyl group originally attached to the sp2-hybridized silicon atom of the silene apparently underwent a 1,2-migration to the adjacent carbon atom (which had been sp2-hybridized in the parent silene). The original trimethylsiloxy group either underwent a reverse 1,2-rearrangement from carbon to silicon, forming 6, or else was eliminated during the reaction, yielding 7. The proportions of products 6 and 7 were found to be insensitive to the amount of Grignard reagent or the temperature at which the reaction occurred but were sensitive to the polarity of the solvent system, more product of structure 6 being formed in less polar solvents. In a related study it was shown that reaction of t-BuLi with a (polysilyl)acylsilane gave rise to a product in which a molecule of t-BuLi had added to a silene formed in the course of the reaction. Mechanisms explaining the formations of these products are given. © 1991 American Chemical Society.
Persistent Identifierhttp://hdl.handle.net/10722/167307
ISSN
2015 Impact Factor: 4.186
2015 SCImago Journal Rankings: 2.043
ISI Accession Number ID

 

DC FieldValueLanguage
dc.contributor.authorBrook, AGen_US
dc.contributor.authorChiu, Pen_US
dc.contributor.authorMcclenaghnan, Jen_US
dc.contributor.authorLough, AJen_US
dc.date.accessioned2012-10-08T03:05:30Z-
dc.date.available2012-10-08T03:05:30Z-
dc.date.issued1991en_US
dc.identifier.citationOrganometallics, 1991, v. 10 n. 9, p. 3292-3301en_US
dc.identifier.issn0276-7333en_US
dc.identifier.urihttp://hdl.handle.net/10722/167307-
dc.description.abstractGrignard reagents have been found to add to members of the family of stable silenes (Me3Si)RSi=C-(OSiMe3)R′ (R = Me3Si, Ph; R′ = Ad or t-Bu). Two types of product were formed, namely a family of compounds where one molecule of Grignard reagent R″MgX was involved, leading to products with the structures 6, Me3SiOSiRR″CHR′(SiMe3), and a family where two molecules of Grignard reagent were involved, leading to products with structures 7, RR″2SiCHR′(SiMe3). The crystal structure of one compound, 6baa (R = Ph, R′ = Ad, R″ = Me), was obtained, confirming the structure assigned to this family of compounds. It is evident that, in the course of forming these products, a trimethylsilyl group originally attached to the sp2-hybridized silicon atom of the silene apparently underwent a 1,2-migration to the adjacent carbon atom (which had been sp2-hybridized in the parent silene). The original trimethylsiloxy group either underwent a reverse 1,2-rearrangement from carbon to silicon, forming 6, or else was eliminated during the reaction, yielding 7. The proportions of products 6 and 7 were found to be insensitive to the amount of Grignard reagent or the temperature at which the reaction occurred but were sensitive to the polarity of the solvent system, more product of structure 6 being formed in less polar solvents. In a related study it was shown that reaction of t-BuLi with a (polysilyl)acylsilane gave rise to a product in which a molecule of t-BuLi had added to a silene formed in the course of the reaction. Mechanisms explaining the formations of these products are given. © 1991 American Chemical Society.en_US
dc.languageengen_US
dc.publisherAmerican Chemical Society. The Journal's web site is located at http://pubs.acs.org/organometallicsen_US
dc.relation.ispartofOrganometallicsen_US
dc.titleReactions of stable silenes with Grignard reagentsen_US
dc.typeArticleen_US
dc.identifier.emailChiu, P:pchiu@hku.hken_US
dc.identifier.authorityChiu, P=rp00680en_US
dc.description.naturelink_to_subscribed_fulltexten_US
dc.identifier.doi10.1021/om00055a056-
dc.identifier.scopuseid_2-s2.0-0000889046en_US
dc.identifier.volume10en_US
dc.identifier.issue9en_US
dc.identifier.spage3292en_US
dc.identifier.epage3301en_US
dc.identifier.isiWOS:A1991GF40500056-
dc.publisher.placeUnited Statesen_US
dc.identifier.scopusauthoridBrook, AG=16035426500en_US
dc.identifier.scopusauthoridChiu, P=11140148700en_US
dc.identifier.scopusauthoridMcClenaghnan, J=15079258000en_US
dc.identifier.scopusauthoridLough, AJ=35467423800en_US

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