Stable GaX2, InX2 and TlX2 radicals.
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 de...
| Main Authors: | , , , , , , , , , , , , |
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| Format: | Journal article |
| Language: | English |
| Published: |
Nature Publishing Group
2014
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| _version_ | 1826258956911116288 |
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| author | Protchenko, A Dange, D Harmer, JR Tang, C Schwarz, A Kelly, M Phillips, N Tirfoin, R Birjkumar, K Jones, C Kaltsoyannis, N Mountford, P Aldridge, S |
| author_facet | Protchenko, A Dange, D Harmer, JR Tang, C Schwarz, A Kelly, M Phillips, N Tirfoin, R Birjkumar, K Jones, C Kaltsoyannis, N Mountford, P Aldridge, S |
| author_sort | Protchenko, A |
| collection | OXFORD |
| description | 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. |
| first_indexed | 2024-03-06T18:42:16Z |
| format | Journal article |
| id | oxford-uuid:0d4b1286-fbbe-4ec4-bc16-03b05350c017 |
| institution | University of Oxford |
| language | English |
| last_indexed | 2024-03-06T18:42:16Z |
| publishDate | 2014 |
| publisher | Nature Publishing Group |
| record_format | dspace |
| spelling | oxford-uuid:0d4b1286-fbbe-4ec4-bc16-03b05350c0172022-03-26T09:39:43ZStable GaX2, InX2 and TlX2 radicals.Journal articlehttp://purl.org/coar/resource_type/c_dcae04bcuuid:0d4b1286-fbbe-4ec4-bc16-03b05350c017EnglishSymplectic Elements at OxfordNature Publishing Group2014Protchenko, ADange, DHarmer, JRTang, CSchwarz, AKelly, MPhillips, NTirfoin, RBirjkumar, KJones, CKaltsoyannis, NMountford, PAldridge, SThe 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. |
| spellingShingle | Protchenko, A Dange, D Harmer, JR Tang, C Schwarz, A Kelly, M Phillips, N Tirfoin, R Birjkumar, K Jones, C Kaltsoyannis, N Mountford, P Aldridge, S Stable GaX2, InX2 and TlX2 radicals. |
| title | Stable GaX2, InX2 and TlX2 radicals. |
| title_full | Stable GaX2, InX2 and TlX2 radicals. |
| title_fullStr | Stable GaX2, InX2 and TlX2 radicals. |
| title_full_unstemmed | Stable GaX2, InX2 and TlX2 radicals. |
| title_short | Stable GaX2, InX2 and TlX2 radicals. |
| title_sort | stable gax2 inx2 and tlx2 radicals |
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