Stable GaX2, InX2 and TlX2 radicals.
Identifieur interne : 000042 ( Main/Exploration ); précédent : 000041; suivant : 000043Stable GaX2, InX2 and TlX2 radicals.
Auteurs : RBID : pubmed:24651198Abstract
The chemistry of the Group 13 metals is dominated by the +1 and +3 oxidation states, and simple monomeric M(II) species are typically short-lived, highly reactive species. Here we report the first thermally robust monomeric MX2 radicals of gallium, indium and thallium. By making use of sterically demanding boryl substituents, compounds of the type M(II)(boryl)2 (M = Ga, In, Tl) can be synthesized. These decompose above 130 °C and are amenable to structural characterization in the solid state by X-ray crystallography. Electron paramagnetic resonance and computational studies reveal a dominant metal-centred character for all three radicals (>70% spin density at the metal). M(II) species have been invoked as key short-lived intermediates in well-known electron-transfer processes; consistently, the chemical behaviour of these novel isolated species reveals facile one-electron shuttling processes at the metal centre.
DOI: 10.1038/nchem.1870
PubMed: 24651198
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3800</wicri:regionArea></affiliation></author><author><name sortKey="Harmer, Jeffrey R" uniqKey="Harmer J">Jeffrey R Harmer</name><affiliation wicri:level="1"><nlm:affiliation>1] Centre for Advanced Electron Spin Resonance, Department of Chemistry, University of Oxford, South Parks Road, Oxford OX1 3QR [2] Center for Advanced Imaging, University of Queensland, St Lucia, Queensland 4072, Australia.</nlm:affiliation><country xml:lang="fr">Australie</country><wicri:regionArea>1] Centre for Advanced Electron Spin Resonance, Department of Chemistry, University of Oxford, South Parks Road, Oxford OX1 3QR [2] Center for Advanced Imaging, University of Queensland, St Lucia, Queensland 4072</wicri:regionArea></affiliation></author><author><name sortKey="Tang, Christina Y" uniqKey="Tang C">Christina Y Tang</name><affiliation wicri:level="1"><nlm:affiliation>Inorganic Chemistry Laboratory, Department of Chemistry, University of Oxford, South Parks Road, Oxford OX1 3QR, UK.</nlm:affiliation><country xml:lang="fr">Royaume-Uni</country><wicri:regionArea>Inorganic Chemistry Laboratory, Department of Chemistry, University of Oxford, South Parks Road, Oxford OX1 3QR</wicri:regionArea></affiliation></author><author><name sortKey="Schwarz, Andrew D" uniqKey="Schwarz A">Andrew D Schwarz</name><affiliation wicri:level="1"><nlm:affiliation>Inorganic Chemistry Laboratory, Department of Chemistry, University of Oxford, South Parks Road, Oxford OX1 3QR, UK.</nlm:affiliation><country xml:lang="fr">Royaume-Uni</country><wicri:regionArea>Inorganic Chemistry Laboratory, Department of Chemistry, University of Oxford, South Parks Road, Oxford OX1 3QR</wicri:regionArea></affiliation></author><author><name sortKey="Kelly, Michael J" uniqKey="Kelly M">Michael J Kelly</name><affiliation wicri:level="1"><nlm:affiliation>Inorganic Chemistry Laboratory, Department of Chemistry, University of Oxford, South Parks Road, Oxford OX1 3QR, UK.</nlm:affiliation><country xml:lang="fr">Royaume-Uni</country><wicri:regionArea>Inorganic Chemistry Laboratory, Department of Chemistry, University of Oxford, South Parks Road, Oxford OX1 3QR</wicri:regionArea></affiliation></author><author><name sortKey="Phillips, Nicholas" uniqKey="Phillips N">Nicholas Phillips</name><affiliation wicri:level="1"><nlm:affiliation>Inorganic Chemistry Laboratory, Department of Chemistry, University of Oxford, South Parks Road, Oxford OX1 3QR, UK.</nlm:affiliation><country xml:lang="fr">Royaume-Uni</country><wicri:regionArea>Inorganic Chemistry Laboratory, Department of Chemistry, University of Oxford, South Parks Road, Oxford OX1 3QR</wicri:regionArea></affiliation></author><author><name sortKey="Tirfoin, Remi" uniqKey="Tirfoin R">Remi Tirfoin</name><affiliation wicri:level="1"><nlm:affiliation>Inorganic Chemistry Laboratory, Department of Chemistry, University of Oxford, South Parks Road, Oxford OX1 3QR, UK.</nlm:affiliation><country 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xml:lang="fr">Australie</country><wicri:regionArea>School of Chemistry, PO Box 23, Monash University, Melbourne, Victoria 3800</wicri:regionArea></affiliation></author><author><name sortKey="Kaltsoyannis, Nikolas" uniqKey="Kaltsoyannis N">Nikolas Kaltsoyannis</name><affiliation wicri:level="1"><nlm:affiliation>Department of Chemistry, University College London, Christopher Ingold Laboratories, 20 Gordon Street, London WC1H 0AJ, UK.</nlm:affiliation><country xml:lang="fr">Royaume-Uni</country><wicri:regionArea>Department of Chemistry, University College London, Christopher Ingold Laboratories, 20 Gordon Street, London WC1H 0AJ</wicri:regionArea></affiliation></author><author><name sortKey="Mountford, Philip" uniqKey="Mountford P">Philip Mountford</name><affiliation wicri:level="1"><nlm:affiliation>Inorganic Chemistry Laboratory, Department of Chemistry, University of Oxford, South Parks Road, Oxford OX1 3QR, UK.</nlm:affiliation><country xml:lang="fr">Royaume-Uni</country><wicri:regionArea>Inorganic Chemistry Laboratory, Department of Chemistry, University of Oxford, South Parks Road, Oxford OX1 3QR</wicri:regionArea></affiliation></author><author><name sortKey="Aldridge, Simon" uniqKey="Aldridge S">Simon Aldridge</name><affiliation wicri:level="1"><nlm:affiliation>Inorganic Chemistry Laboratory, Department of Chemistry, University of Oxford, South Parks Road, Oxford OX1 3QR, UK.</nlm:affiliation><country xml:lang="fr">Royaume-Uni</country><wicri:regionArea>Inorganic Chemistry Laboratory, Department of Chemistry, University of Oxford, South Parks Road, Oxford OX1 3QR</wicri:regionArea></affiliation></author></titleStmt><publicationStmt><date when="2014">2014</date><idno type="doi">10.1038/nchem.1870</idno><idno type="RBID">pubmed:24651198</idno><idno type="pmid">24651198</idno><idno type="wicri:Area/Main/Corpus">000105</idno><idno type="wicri:Area/Main/Curation">000105</idno><idno type="wicri:Area/Main/Exploration">000042</idno></publicationStmt></fileDesc><profileDesc><textClass></textClass></profileDesc></teiHeader><front><div type="abstract" xml:lang="en">The chemistry of the Group 13 metals is dominated by the +1 and +3 oxidation states, and simple monomeric M(II) species are typically short-lived, highly reactive species. Here we report the first thermally robust monomeric MX2 radicals of gallium, indium and thallium. By making use of sterically demanding boryl substituents, compounds of the type M(II)(boryl)2 (M = Ga, In, Tl) can be synthesized. These decompose above 130 °C and are amenable to structural characterization in the solid state by X-ray crystallography. Electron paramagnetic resonance and computational studies reveal a dominant metal-centred character for all three radicals (>70% spin density at the metal). M(II) species have been invoked as key short-lived intermediates in well-known electron-transfer processes; consistently, the chemical behaviour of these novel isolated species reveals facile one-electron shuttling processes at the metal centre.</div></front></TEI><pubmed><MedlineCitation Owner="NLM" Status="In-Process"><PMID Version="1">24651198</PMID><DateCreated><Year>2014</Year><Month>03</Month><Day>21</Day></DateCreated><Article PubModel="Print-Electronic"><Journal><ISSN IssnType="Electronic">1755-4349</ISSN><JournalIssue CitedMedium="Internet"><Volume>6</Volume><Issue>4</Issue><PubDate><Year>2014</Year><Month>Apr</Month></PubDate></JournalIssue><Title>Nature chemistry</Title><ISOAbbreviation>Nat Chem</ISOAbbreviation></Journal><ArticleTitle>Stable GaX2, InX2 and TlX2 radicals.</ArticleTitle><Pagination><MedlinePgn>315-9</MedlinePgn></Pagination><ELocationID EIdType="doi" ValidYN="Y">10.1038/nchem.1870</ELocationID><Abstract><AbstractText>The chemistry of the Group 13 metals is dominated by the +1 and +3 oxidation states, and simple monomeric M(II) species are typically short-lived, highly reactive species. Here we report the first thermally robust monomeric MX2 radicals of gallium, indium and thallium. By making use of sterically demanding boryl substituents, compounds of the type M(II)(boryl)2 (M = Ga, In, Tl) can be synthesized. These decompose above 130 °C and are amenable to structural characterization in the solid state by X-ray crystallography. Electron paramagnetic resonance and computational studies reveal a dominant metal-centred character for all three radicals (>70% spin density at the metal). M(II) species have been invoked as key short-lived intermediates in well-known electron-transfer processes; consistently, the chemical behaviour of these novel isolated species reveals facile one-electron shuttling processes at the metal centre.</AbstractText></Abstract><AuthorList CompleteYN="Y"><Author ValidYN="Y"><LastName>Protchenko</LastName><ForeName>Andrey V</ForeName><Initials>AV</Initials><Affiliation>Inorganic Chemistry Laboratory, Department of Chemistry, University of Oxford, South Parks Road, Oxford OX1 3QR, UK.</Affiliation></Author><Author ValidYN="Y"><LastName>Dange</LastName><ForeName>Deepak</ForeName><Initials>D</Initials><Affiliation>School of Chemistry, PO Box 23, Monash University, Melbourne, Victoria 3800, Australia.</Affiliation></Author><Author ValidYN="Y"><LastName>Harmer</LastName><ForeName>Jeffrey R</ForeName><Initials>JR</Initials><Affiliation>1] Centre for Advanced Electron Spin Resonance, Department of Chemistry, University of Oxford, South Parks Road, Oxford OX1 3QR [2] Center for Advanced Imaging, University of Queensland, St Lucia, Queensland 4072, Australia.</Affiliation></Author><Author ValidYN="Y"><LastName>Tang</LastName><ForeName>Christina Y</ForeName><Initials>CY</Initials><Affiliation>Inorganic Chemistry Laboratory, Department of Chemistry, University of Oxford, South Parks Road, Oxford OX1 3QR, UK.</Affiliation></Author><Author ValidYN="Y"><LastName>Schwarz</LastName><ForeName>Andrew D</ForeName><Initials>AD</Initials><Affiliation>Inorganic Chemistry Laboratory, Department of Chemistry, University of Oxford, South Parks Road, Oxford OX1 3QR, UK.</Affiliation></Author><Author ValidYN="Y"><LastName>Kelly</LastName><ForeName>Michael J</ForeName><Initials>MJ</Initials><Affiliation>Inorganic Chemistry Laboratory, Department of Chemistry, University of Oxford, South Parks Road, Oxford OX1 3QR, UK.</Affiliation></Author><Author ValidYN="Y"><LastName>Phillips</LastName><ForeName>Nicholas</ForeName><Initials>N</Initials><Affiliation>Inorganic Chemistry Laboratory, Department of Chemistry, University of Oxford, South Parks Road, Oxford OX1 3QR, UK.</Affiliation></Author><Author ValidYN="Y"><LastName>Tirfoin</LastName><ForeName>Remi</ForeName><Initials>R</Initials><Affiliation>Inorganic Chemistry Laboratory, Department of Chemistry, University of Oxford, South Parks Road, Oxford OX1 3QR, UK.</Affiliation></Author><Author ValidYN="Y"><LastName>Birjkumar</LastName><ForeName>Krishna Hassomal</ForeName><Initials>KH</Initials><Affiliation>Department of Chemistry, University College London, Christopher Ingold Laboratories, 20 Gordon Street, London WC1H 0AJ, UK.</Affiliation></Author><Author ValidYN="Y"><LastName>Jones</LastName><ForeName>Cameron</ForeName><Initials>C</Initials><Affiliation>School of Chemistry, PO Box 23, Monash University, Melbourne, Victoria 3800, Australia.</Affiliation></Author><Author ValidYN="Y"><LastName>Kaltsoyannis</LastName><ForeName>Nikolas</ForeName><Initials>N</Initials><Affiliation>Department of Chemistry, University College London, Christopher Ingold Laboratories, 20 Gordon Street, London WC1H 0AJ, UK.</Affiliation></Author><Author ValidYN="Y"><LastName>Mountford</LastName><ForeName>Philip</ForeName><Initials>P</Initials><Affiliation>Inorganic Chemistry Laboratory, Department of Chemistry, University of Oxford, South Parks Road, Oxford OX1 3QR, UK.</Affiliation></Author><Author ValidYN="Y"><LastName>Aldridge</LastName><ForeName>Simon</ForeName><Initials>S</Initials><Affiliation>Inorganic Chemistry Laboratory, Department of Chemistry, University of Oxford, South Parks Road, Oxford OX1 3QR, UK.</Affiliation></Author></AuthorList><Language>eng</Language><DataBankList 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