Gas-phase ion chemistry of silyl cations obtained from hexamethyldisilazane
Autor(a) principal: | |
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Data de Publicação: | 2002 |
Outros Autores: | , |
Tipo de documento: | Artigo |
Idioma: | eng |
Título da fonte: | Química Nova (Online) |
Texto Completo: | http://old.scielo.br/scielo.php?script=sci_arttext&pid=S0100-40422002000500012 |
Resumo: | The gas-phase ion-molecule reactions of the Me3SiN(H)SiMe2+ ion, obtained by electron ionization from Me3SiN(H)SiMe3, have been studied in a Fourier transform ion cyclotron resonance spectrometer in order to understand the mechanistic details of an important chemical system presently used in film formation. This silyl cation has been observed to undergo addition reactions at electron rich centers to form stable adducts that may undergo further methane elimination in the case of alcohols and amines. The most important feature of these reactions is the fact that a metathesis type reaction can be observed in the presence of H2O, and other hydrogen labile substrates like alcohols, leading to the formation of the corresponding oxygen-containing ion, i.e. Me3SiOSiMe2+. For alcohols (ROH), facile formation of a tertiary product ion, presumably corresponding to an Me3Si-O-Si(Me)=O+-R structure with elimination of an amine reveals the strong tendency of these nitrogen-containing ions to undergo metathesis type reactions with oxygen containing substrates. |
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Gas-phase ion chemistry of silyl cations obtained from hexamethyldisilazanehexamethyldisilazanegas phase ion chemistrysilyl cation additionThe gas-phase ion-molecule reactions of the Me3SiN(H)SiMe2+ ion, obtained by electron ionization from Me3SiN(H)SiMe3, have been studied in a Fourier transform ion cyclotron resonance spectrometer in order to understand the mechanistic details of an important chemical system presently used in film formation. This silyl cation has been observed to undergo addition reactions at electron rich centers to form stable adducts that may undergo further methane elimination in the case of alcohols and amines. The most important feature of these reactions is the fact that a metathesis type reaction can be observed in the presence of H2O, and other hydrogen labile substrates like alcohols, leading to the formation of the corresponding oxygen-containing ion, i.e. Me3SiOSiMe2+. For alcohols (ROH), facile formation of a tertiary product ion, presumably corresponding to an Me3Si-O-Si(Me)=O+-R structure with elimination of an amine reveals the strong tendency of these nitrogen-containing ions to undergo metathesis type reactions with oxygen containing substrates.Sociedade Brasileira de Química2002-09-01info:eu-repo/semantics/articleinfo:eu-repo/semantics/publishedVersiontext/htmlhttp://old.scielo.br/scielo.php?script=sci_arttext&pid=S0100-40422002000500012Química Nova v.25 n.5 2002reponame:Química Nova (Online)instname:Sociedade Brasileira de Química (SBQ)instacron:SBQ10.1590/S0100-40422002000500012info:eu-repo/semantics/openAccessXavier,Luciano A.Ambra,SofiaRiveros,José M.eng2002-11-13T00:00:00Zoai:scielo:S0100-40422002000500012Revistahttps://www.scielo.br/j/qn/ONGhttps://old.scielo.br/oai/scielo-oai.phpquimicanova@sbq.org.br1678-70640100-4042opendoar:2002-11-13T00:00Química Nova (Online) - Sociedade Brasileira de Química (SBQ)false |
dc.title.none.fl_str_mv |
Gas-phase ion chemistry of silyl cations obtained from hexamethyldisilazane |
title |
Gas-phase ion chemistry of silyl cations obtained from hexamethyldisilazane |
spellingShingle |
Gas-phase ion chemistry of silyl cations obtained from hexamethyldisilazane Xavier,Luciano A. hexamethyldisilazane gas phase ion chemistry silyl cation addition |
title_short |
Gas-phase ion chemistry of silyl cations obtained from hexamethyldisilazane |
title_full |
Gas-phase ion chemistry of silyl cations obtained from hexamethyldisilazane |
title_fullStr |
Gas-phase ion chemistry of silyl cations obtained from hexamethyldisilazane |
title_full_unstemmed |
Gas-phase ion chemistry of silyl cations obtained from hexamethyldisilazane |
title_sort |
Gas-phase ion chemistry of silyl cations obtained from hexamethyldisilazane |
author |
Xavier,Luciano A. |
author_facet |
Xavier,Luciano A. Ambra,Sofia Riveros,José M. |
author_role |
author |
author2 |
Ambra,Sofia Riveros,José M. |
author2_role |
author author |
dc.contributor.author.fl_str_mv |
Xavier,Luciano A. Ambra,Sofia Riveros,José M. |
dc.subject.por.fl_str_mv |
hexamethyldisilazane gas phase ion chemistry silyl cation addition |
topic |
hexamethyldisilazane gas phase ion chemistry silyl cation addition |
description |
The gas-phase ion-molecule reactions of the Me3SiN(H)SiMe2+ ion, obtained by electron ionization from Me3SiN(H)SiMe3, have been studied in a Fourier transform ion cyclotron resonance spectrometer in order to understand the mechanistic details of an important chemical system presently used in film formation. This silyl cation has been observed to undergo addition reactions at electron rich centers to form stable adducts that may undergo further methane elimination in the case of alcohols and amines. The most important feature of these reactions is the fact that a metathesis type reaction can be observed in the presence of H2O, and other hydrogen labile substrates like alcohols, leading to the formation of the corresponding oxygen-containing ion, i.e. Me3SiOSiMe2+. For alcohols (ROH), facile formation of a tertiary product ion, presumably corresponding to an Me3Si-O-Si(Me)=O+-R structure with elimination of an amine reveals the strong tendency of these nitrogen-containing ions to undergo metathesis type reactions with oxygen containing substrates. |
publishDate |
2002 |
dc.date.none.fl_str_mv |
2002-09-01 |
dc.type.driver.fl_str_mv |
info:eu-repo/semantics/article |
dc.type.status.fl_str_mv |
info:eu-repo/semantics/publishedVersion |
format |
article |
status_str |
publishedVersion |
dc.identifier.uri.fl_str_mv |
http://old.scielo.br/scielo.php?script=sci_arttext&pid=S0100-40422002000500012 |
url |
http://old.scielo.br/scielo.php?script=sci_arttext&pid=S0100-40422002000500012 |
dc.language.iso.fl_str_mv |
eng |
language |
eng |
dc.relation.none.fl_str_mv |
10.1590/S0100-40422002000500012 |
dc.rights.driver.fl_str_mv |
info:eu-repo/semantics/openAccess |
eu_rights_str_mv |
openAccess |
dc.format.none.fl_str_mv |
text/html |
dc.publisher.none.fl_str_mv |
Sociedade Brasileira de Química |
publisher.none.fl_str_mv |
Sociedade Brasileira de Química |
dc.source.none.fl_str_mv |
Química Nova v.25 n.5 2002 reponame:Química Nova (Online) instname:Sociedade Brasileira de Química (SBQ) instacron:SBQ |
instname_str |
Sociedade Brasileira de Química (SBQ) |
instacron_str |
SBQ |
institution |
SBQ |
reponame_str |
Química Nova (Online) |
collection |
Química Nova (Online) |
repository.name.fl_str_mv |
Química Nova (Online) - Sociedade Brasileira de Química (SBQ) |
repository.mail.fl_str_mv |
quimicanova@sbq.org.br |
_version_ |
1750318102739943424 |