Oxidation state, aggregation, and heterolytic dissociation of allyl indium reagents.
Identifieur interne : 001832 ( Main/Exploration ); précédent : 001831; suivant : 001833Oxidation state, aggregation, and heterolytic dissociation of allyl indium reagents.
Auteurs : RBID : pubmed:20377261English descriptors
- KwdEn :
- MESH :
- chemical , chemistry : Allyl Compounds, Formamides, Furans, Indium, Iodides, Water.
- chemical : Dimethylformamide, Solutions.
- Oxidation-Reduction, Spectrometry, Mass, Electrospray Ionization.
Abstract
Solutions of allyl indium reagents formed in the reactions of indium with allyl bromide and allyl iodide, respectively, in N,N-dimethylformamide, tetrahydrofuran, and water were analyzed by a combination of electrospray-ionization mass spectrometry, temperature-dependent (1)H NMR spectroscopy, and electrical conductivity measurements. Additional mass spectrometric experiments probed charge-tagged derivatives of the allyl indium reagents. The results obtained indicate the presence of allyl indium(+3) species, which undergo heterolytic dissociation to yield ions such as InR(2)(solv)(+) and InRX(3)(-) with R = allyl and X = Br and I. The extent of dissociation is greatest for N,N-dimethylformamide, whereas aggregation effects are more pronounced for the less polar tetrahydrofuran. The heterolytic dissociation of the allyl indium reagents supposedly enhances their reactivity by simultaneously providing highly Lewis acidic allyl indium cations and nucleophilic allyl indate anions.
DOI: 10.1021/ja908101j
PubMed: 20377261
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<record><TEI><teiHeader><fileDesc><titleStmt><title xml:lang="en">Oxidation state, aggregation, and heterolytic dissociation of allyl indium reagents.</title><author><name sortKey="Koszinowski, Konrad" uniqKey="Koszinowski K">Konrad Koszinowski</name><affiliation wicri:level="3"><nlm:affiliation>Department Chemie, Ludwig-Maximilians-Universität München, Butenandtstr. 5-13, 81377 München, Germany. konrad.koszinowski@cup.uni-muenchen.de</nlm:affiliation><country xml:lang="fr">Allemagne</country><wicri:regionArea>Department Chemie, Ludwig-Maximilians-Universität München, Butenandtstr. 5-13, 81377 München</wicri:regionArea><placeName><region type="land" nuts="1">Bavière</region><region type="district" nuts="2">District de Haute-Bavière</region><settlement type="city">Munich</settlement></placeName></affiliation></author></titleStmt><publicationStmt><date when="2010">2010</date><idno type="doi">10.1021/ja908101j</idno><idno type="RBID">pubmed:20377261</idno><idno type="pmid">20377261</idno><idno type="wicri:Area/Main/Corpus">001987</idno><idno type="wicri:Area/Main/Curation">001987</idno><idno type="wicri:Area/Main/Exploration">001832</idno></publicationStmt></fileDesc><profileDesc><textClass><keywords scheme="KwdEn" xml:lang="en"><term>Allyl Compounds (chemistry)</term><term>Dimethylformamide</term><term>Formamides (chemistry)</term><term>Furans (chemistry)</term><term>Indium (chemistry)</term><term>Iodides (chemistry)</term><term>Oxidation-Reduction</term><term>Solutions</term><term>Spectrometry, Mass, Electrospray Ionization</term><term>Water (chemistry)</term></keywords><keywords scheme="MESH" type="chemical" qualifier="chemistry" xml:lang="en"><term>Allyl Compounds</term><term>Formamides</term><term>Furans</term><term>Indium</term><term>Iodides</term><term>Water</term></keywords><keywords scheme="MESH" type="chemical" xml:lang="en"><term>Dimethylformamide</term><term>Solutions</term></keywords><keywords scheme="MESH" xml:lang="en"><term>Oxidation-Reduction</term><term>Spectrometry, Mass, Electrospray Ionization</term></keywords></textClass></profileDesc></teiHeader><front><div type="abstract" xml:lang="en">Solutions of allyl indium reagents formed in the reactions of indium with allyl bromide and allyl iodide, respectively, in N,N-dimethylformamide, tetrahydrofuran, and water were analyzed by a combination of electrospray-ionization mass spectrometry, temperature-dependent (1)H NMR spectroscopy, and electrical conductivity measurements. Additional mass spectrometric experiments probed charge-tagged derivatives of the allyl indium reagents. The results obtained indicate the presence of allyl indium(+3) species, which undergo heterolytic dissociation to yield ions such as InR(2)(solv)(+) and InRX(3)(-) with R = allyl and X = Br and I. The extent of dissociation is greatest for N,N-dimethylformamide, whereas aggregation effects are more pronounced for the less polar tetrahydrofuran. The heterolytic dissociation of the allyl indium reagents supposedly enhances their reactivity by simultaneously providing highly Lewis acidic allyl indium cations and nucleophilic allyl indate anions.</div></front></TEI><pubmed><MedlineCitation Owner="NLM" Status="MEDLINE"><PMID Version="1">20377261</PMID><DateCreated><Year>2010</Year><Month>04</Month><Day>28</Day></DateCreated><DateCompleted><Year>2010</Year><Month>07</Month><Day>27</Day></DateCompleted><DateRevised><Year>2013</Year><Month>11</Month><Day>21</Day></DateRevised><Article PubModel="Print"><Journal><ISSN IssnType="Electronic">1520-5126</ISSN><JournalIssue CitedMedium="Internet"><Volume>132</Volume><Issue>17</Issue><PubDate><Year>2010</Year><Month>May</Month><Day>5</Day></PubDate></JournalIssue><Title>Journal of the American Chemical Society</Title><ISOAbbreviation>J. Am. Chem. Soc.</ISOAbbreviation></Journal><ArticleTitle>Oxidation state, aggregation, and heterolytic dissociation of allyl indium reagents.</ArticleTitle><Pagination><MedlinePgn>6032-40</MedlinePgn></Pagination><ELocationID EIdType="doi" ValidYN="Y">10.1021/ja908101j</ELocationID><Abstract><AbstractText>Solutions of allyl indium reagents formed in the reactions of indium with allyl bromide and allyl iodide, respectively, in N,N-dimethylformamide, tetrahydrofuran, and water were analyzed by a combination of electrospray-ionization mass spectrometry, temperature-dependent (1)H NMR spectroscopy, and electrical conductivity measurements. Additional mass spectrometric experiments probed charge-tagged derivatives of the allyl indium reagents. The results obtained indicate the presence of allyl indium(+3) species, which undergo heterolytic dissociation to yield ions such as InR(2)(solv)(+) and InRX(3)(-) with R = allyl and X = Br and I. The extent of dissociation is greatest for N,N-dimethylformamide, whereas aggregation effects are more pronounced for the less polar tetrahydrofuran. The heterolytic dissociation of the allyl indium reagents supposedly enhances their reactivity by simultaneously providing highly Lewis acidic allyl indium cations and nucleophilic allyl indate anions.</AbstractText></Abstract><AuthorList CompleteYN="Y"><Author ValidYN="Y"><LastName>Koszinowski</LastName><ForeName>Konrad</ForeName><Initials>K</Initials><Affiliation>Department Chemie, Ludwig-Maximilians-Universität München, Butenandtstr. 5-13, 81377 München, Germany. konrad.koszinowski@cup.uni-muenchen.de</Affiliation></Author></AuthorList><Language>eng</Language><PublicationTypeList><PublicationType>Journal Article</PublicationType><PublicationType>Research Support, Non-U.S. Gov't</PublicationType></PublicationTypeList></Article><MedlineJournalInfo><Country>United States</Country><MedlineTA>J Am Chem Soc</MedlineTA><NlmUniqueID>7503056</NlmUniqueID><ISSNLinking>0002-7863</ISSNLinking></MedlineJournalInfo><ChemicalList><Chemical><RegistryNumber>0</RegistryNumber><NameOfSubstance>Allyl Compounds</NameOfSubstance></Chemical><Chemical><RegistryNumber>0</RegistryNumber><NameOfSubstance>Formamides</NameOfSubstance></Chemical><Chemical><RegistryNumber>0</RegistryNumber><NameOfSubstance>Furans</NameOfSubstance></Chemical><Chemical><RegistryNumber>0</RegistryNumber><NameOfSubstance>Iodides</NameOfSubstance></Chemical><Chemical><RegistryNumber>0</RegistryNumber><NameOfSubstance>Solutions</NameOfSubstance></Chemical><Chemical><RegistryNumber>045A6V3VFX</RegistryNumber><NameOfSubstance>Indium</NameOfSubstance></Chemical><Chemical><RegistryNumber>059QF0KO0R</RegistryNumber><NameOfSubstance>Water</NameOfSubstance></Chemical><Chemical><RegistryNumber>3N8FZZ6PY4</RegistryNumber><NameOfSubstance>tetrahydrofuran</NameOfSubstance></Chemical><Chemical><RegistryNumber>8696NH0Y2X</RegistryNumber><NameOfSubstance>Dimethylformamide</NameOfSubstance></Chemical><Chemical><RegistryNumber>FXQ8X2F74Z</RegistryNumber><NameOfSubstance>allyl bromide</NameOfSubstance></Chemical></ChemicalList><CitationSubset>IM</CitationSubset><MeshHeadingList><MeshHeading><DescriptorName MajorTopicYN="N">Allyl Compounds</DescriptorName><QualifierName MajorTopicYN="Y">chemistry</QualifierName></MeshHeading><MeshHeading><DescriptorName MajorTopicYN="N">Dimethylformamide</DescriptorName></MeshHeading><MeshHeading><DescriptorName MajorTopicYN="N">Formamides</DescriptorName><QualifierName MajorTopicYN="N">chemistry</QualifierName></MeshHeading><MeshHeading><DescriptorName MajorTopicYN="N">Furans</DescriptorName><QualifierName MajorTopicYN="N">chemistry</QualifierName></MeshHeading><MeshHeading><DescriptorName MajorTopicYN="N">Indium</DescriptorName><QualifierName MajorTopicYN="Y">chemistry</QualifierName></MeshHeading><MeshHeading><DescriptorName MajorTopicYN="N">Iodides</DescriptorName><QualifierName MajorTopicYN="N">chemistry</QualifierName></MeshHeading><MeshHeading><DescriptorName MajorTopicYN="N">Oxidation-Reduction</DescriptorName></MeshHeading><MeshHeading><DescriptorName MajorTopicYN="N">Solutions</DescriptorName></MeshHeading><MeshHeading><DescriptorName MajorTopicYN="N">Spectrometry, Mass, Electrospray Ionization</DescriptorName></MeshHeading><MeshHeading><DescriptorName MajorTopicYN="N">Water</DescriptorName><QualifierName MajorTopicYN="N">chemistry</QualifierName></MeshHeading></MeshHeadingList></MedlineCitation><PubmedData><History><PubMedPubDate PubStatus="entrez"><Year>2010</Year><Month>4</Month><Day>10</Day><Hour>6</Hour><Minute>0</Minute></PubMedPubDate><PubMedPubDate PubStatus="pubmed"><Year>2010</Year><Month>4</Month><Day>10</Day><Hour>6</Hour><Minute>0</Minute></PubMedPubDate><PubMedPubDate PubStatus="medline"><Year>2010</Year><Month>7</Month><Day>28</Day><Hour>6</Hour><Minute>0</Minute></PubMedPubDate></History><PublicationStatus>ppublish</PublicationStatus><ArticleIdList><ArticleId IdType="doi">10.1021/ja908101j</ArticleId><ArticleId IdType="pubmed">20377261</ArticleId></ArticleIdList></PubmedData></pubmed></record>Pour manipuler ce document sous Unix (Dilib)
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