Univalent gallium and indium phosphane complexes: from pyramidal M(PPh3)3(+) to carbene-analogous bent M(PtBu3)2(+) (M=Ga, In) complexes.
Identifieur interne : 000952 ( Main/Exploration ); précédent : 000951; suivant : 000953Univalent gallium and indium phosphane complexes: from pyramidal M(PPh3)3(+) to carbene-analogous bent M(PtBu3)2(+) (M=Ga, In) complexes.
Auteurs : RBID : pubmed:22623027Abstract
In a new oxidative route, Ag(+)[Al(OR(F))(4)](-) (R(F)=C(CF(3))(3)) and metallic indium were sonicated in aromatic solvents, such as fluorobenzene (PhF), to give a precipitate of silver metal and highly soluble [In(PhF)(n)](+) salts (n=2, 3) with the weakly coordinating [Al(OR(F))(4)](-) anion in quantitative yield. The In(+) salt and the known analogous Ga(+)[Al(OR(F))(4)](-) were used to synthesize a series of homoleptic PR(3) phosphane complexes [M(PR(3))(n)](+), that is, the weakly PPh(3)-bridged [(Ph(3)P)(3)In-(PPh(3))-In(PPh(3))(3)](2+) that essentially contains two independent [In(PPh(3))(3)](+) cations or, with increasing bulk of the phosphane, the carbene-analogous [M(PtBu(3))(2)](+) (M=Ga, In) cations. The M(I)-P distances are 27 to 29 pm longer for indium, and thus considerably longer than the difference between their tabulated radii (18 pm). The structure, formation, and frontier orbitals of these complexes were investigated by calculations at the BP86/SV(P), B3LYP/def2-TZVPP, MP2/def2-TZVPP, and SCS-MP2/def2-TZVPP levels.
DOI: 10.1002/chem.201104040
PubMed: 22623027
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<record><TEI><teiHeader><fileDesc><titleStmt><title xml:lang="en">Univalent gallium and indium phosphane complexes: from pyramidal M(PPh3)3(+) to carbene-analogous bent M(PtBu3)2(+) (M=Ga, In) complexes.</title><author><name sortKey="Higelin, Alexander" uniqKey="Higelin A">Alexander Higelin</name><affiliation wicri:level="3"><nlm:affiliation>Albert-Ludwigs-Universität Freiburg, Institut für Anorganische und Analytische Chemie, Freiburger Materialforschungszentrum FMF and Freiburg Institute for Advanced Studies FRIAS, Section Soft Matter Science, Albertstrasse 21, 79104 Freiburg, Germany.</nlm:affiliation><country xml:lang="fr">Allemagne</country><wicri:regionArea>Albert-Ludwigs-Universität Freiburg, Institut für Anorganische und Analytische Chemie, Freiburger Materialforschungszentrum FMF and Freiburg Institute for Advanced Studies FRIAS, Section Soft Matter Science, Albertstrasse 21, 79104 Freiburg</wicri:regionArea><placeName><region type="land" nuts="1">Bade-Wurtemberg</region><region type="district" nuts="2">District de Fribourg-en-Brisgau</region><settlement type="city">Fribourg-en-Brisgau</settlement></placeName></affiliation></author><author><name sortKey="Sachs, Ulf" uniqKey="Sachs U">Ulf Sachs</name></author><author><name sortKey="Keller, Sarah" uniqKey="Keller S">Sarah Keller</name></author><author><name sortKey="Krossing, Ingo" uniqKey="Krossing I">Ingo Krossing</name></author></titleStmt><publicationStmt><date when="2012">2012</date><idno type="doi">10.1002/chem.201104040</idno><idno type="RBID">pubmed:22623027</idno><idno type="pmid">22623027</idno><idno type="wicri:Area/Main/Corpus">000C89</idno><idno type="wicri:Area/Main/Curation">000C89</idno><idno type="wicri:Area/Main/Exploration">000952</idno></publicationStmt></fileDesc><profileDesc><textClass></textClass></profileDesc></teiHeader><front><div type="abstract" xml:lang="en">In a new oxidative route, Ag(+)[Al(OR(F))(4)](-) (R(F)=C(CF(3))(3)) and metallic indium were sonicated in aromatic solvents, such as fluorobenzene (PhF), to give a precipitate of silver metal and highly soluble [In(PhF)(n)](+) salts (n=2, 3) with the weakly coordinating [Al(OR(F))(4)](-) anion in quantitative yield. The In(+) salt and the known analogous Ga(+)[Al(OR(F))(4)](-) were used to synthesize a series of homoleptic PR(3) phosphane complexes [M(PR(3))(n)](+), that is, the weakly PPh(3)-bridged [(Ph(3)P)(3)In-(PPh(3))-In(PPh(3))(3)](2+) that essentially contains two independent [In(PPh(3))(3)](+) cations or, with increasing bulk of the phosphane, the carbene-analogous [M(PtBu(3))(2)](+) (M=Ga, In) cations. The M(I)-P distances are 27 to 29 pm longer for indium, and thus considerably longer than the difference between their tabulated radii (18 pm). The structure, formation, and frontier orbitals of these complexes were investigated by calculations at the BP86/SV(P), B3LYP/def2-TZVPP, MP2/def2-TZVPP, and SCS-MP2/def2-TZVPP levels.</div></front></TEI><pubmed><MedlineCitation Owner="NLM" Status="PubMed-not-MEDLINE"><PMID Version="1">22623027</PMID><DateCreated><Year>2012</Year><Month>07</Month><Day>31</Day></DateCreated><DateCompleted><Year>2013</Year><Month>01</Month><Day>04</Day></DateCompleted><Article PubModel="Print-Electronic"><Journal><ISSN IssnType="Electronic">1521-3765</ISSN><JournalIssue CitedMedium="Internet"><Volume>18</Volume><Issue>32</Issue><PubDate><Year>2012</Year><Month>Aug</Month><Day>6</Day></PubDate></JournalIssue><Title>Chemistry (Weinheim an der Bergstrasse, Germany)</Title><ISOAbbreviation>Chemistry</ISOAbbreviation></Journal><ArticleTitle>Univalent gallium and indium phosphane complexes: from pyramidal M(PPh3)3(+) to carbene-analogous bent M(PtBu3)2(+) (M=Ga, In) complexes.</ArticleTitle><Pagination><MedlinePgn>10029-34</MedlinePgn></Pagination><ELocationID EIdType="doi" ValidYN="Y">10.1002/chem.201104040</ELocationID><Abstract><AbstractText>In a new oxidative route, Ag(+)[Al(OR(F))(4)](-) (R(F)=C(CF(3))(3)) and metallic indium were sonicated in aromatic solvents, such as fluorobenzene (PhF), to give a precipitate of silver metal and highly soluble [In(PhF)(n)](+) salts (n=2, 3) with the weakly coordinating [Al(OR(F))(4)](-) anion in quantitative yield. The In(+) salt and the known analogous Ga(+)[Al(OR(F))(4)](-) were used to synthesize a series of homoleptic PR(3) phosphane complexes [M(PR(3))(n)](+), that is, the weakly PPh(3)-bridged [(Ph(3)P)(3)In-(PPh(3))-In(PPh(3))(3)](2+) that essentially contains two independent [In(PPh(3))(3)](+) cations or, with increasing bulk of the phosphane, the carbene-analogous [M(PtBu(3))(2)](+) (M=Ga, In) cations. The M(I)-P distances are 27 to 29 pm longer for indium, and thus considerably longer than the difference between their tabulated radii (18 pm). The structure, formation, and frontier orbitals of these complexes were investigated by calculations at the BP86/SV(P), B3LYP/def2-TZVPP, MP2/def2-TZVPP, and SCS-MP2/def2-TZVPP levels.</AbstractText><CopyrightInformation>Copyright © 2012 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.</CopyrightInformation></Abstract><AuthorList CompleteYN="Y"><Author ValidYN="Y"><LastName>Higelin</LastName><ForeName>Alexander</ForeName><Initials>A</Initials><Affiliation>Albert-Ludwigs-Universität Freiburg, Institut für Anorganische und Analytische Chemie, Freiburger Materialforschungszentrum FMF and Freiburg Institute for Advanced Studies FRIAS, Section Soft Matter Science, Albertstrasse 21, 79104 Freiburg, Germany.</Affiliation></Author><Author ValidYN="Y"><LastName>Sachs</LastName><ForeName>Ulf</ForeName><Initials>U</Initials></Author><Author ValidYN="Y"><LastName>Keller</LastName><ForeName>Sarah</ForeName><Initials>S</Initials></Author><Author ValidYN="Y"><LastName>Krossing</LastName><ForeName>Ingo</ForeName><Initials>I</Initials></Author></AuthorList><Language>eng</Language><PublicationTypeList><PublicationType>Journal Article</PublicationType></PublicationTypeList><ArticleDate DateType="Electronic"><Year>2012</Year><Month>05</Month><Day>23</Day></ArticleDate></Article><MedlineJournalInfo><Country>Germany</Country><MedlineTA>Chemistry</MedlineTA><NlmUniqueID>9513783</NlmUniqueID><ISSNLinking>0947-6539</ISSNLinking></MedlineJournalInfo></MedlineCitation><PubmedData><History><PubMedPubDate PubStatus="received"><Year>2011</Year><Month>12</Month><Day>23</Day></PubMedPubDate><PubMedPubDate PubStatus="revised"><Year>2012</Year><Month>3</Month><Day>23</Day></PubMedPubDate><PubMedPubDate PubStatus="aheadofprint"><Year>2012</Year><Month>5</Month><Day>23</Day></PubMedPubDate><PubMedPubDate PubStatus="entrez"><Year>2012</Year><Month>5</Month><Day>25</Day><Hour>6</Hour><Minute>0</Minute></PubMedPubDate><PubMedPubDate PubStatus="pubmed"><Year>2012</Year><Month>5</Month><Day>25</Day><Hour>6</Hour><Minute>0</Minute></PubMedPubDate><PubMedPubDate PubStatus="medline"><Year>2012</Year><Month>5</Month><Day>25</Day><Hour>6</Hour><Minute>1</Minute></PubMedPubDate></History><PublicationStatus>ppublish</PublicationStatus><ArticleIdList><ArticleId IdType="doi">10.1002/chem.201104040</ArticleId><ArticleId IdType="pubmed">22623027</ArticleId></ArticleIdList></PubmedData></pubmed></record>Pour manipuler ce document sous Unix (Dilib)
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