Infrared spectroscopy of Au+(CH4)n complexes and vibrationally-enhanced C–H activation reactions
A combined spectroscopic and computational study of gas-phase Au+(CH4) n (n = 3–8) complexes reveals a strongly-bound linear Au+(CH4)2 core structure to which up to four additional ligands bind in a secondary coordination shell. Infrared resonance-enhanced photodissociation spectroscopy in the regio...
| Main Authors: | , , , , , |
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| Format: | Journal article |
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Springer US
2017
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| _version_ | 1826306357841625088 |
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| author | Gentleman, A Green, A Price, D Cunningham, E Iskra, A Mackenzie, SR |
| author_facet | Gentleman, A Green, A Price, D Cunningham, E Iskra, A Mackenzie, SR |
| author_sort | Gentleman, A |
| collection | OXFORD |
| description | A combined spectroscopic and computational study of gas-phase Au+(CH4) n (n = 3–8) complexes reveals a strongly-bound linear Au+(CH4)2 core structure to which up to four additional ligands bind in a secondary coordination shell. Infrared resonance-enhanced photodissociation spectroscopy in the region of the CH4 a 1 and t 2 fundamental transitions reveals essentially free internal rotation of the core ligands about the H4C–Au+–CH4 axis, with sharp spectral features assigned by comparison with spectral simulations based on density functional theory. In separate experiments, vibrationally-enhanced dehydrogenation is observed when the t 2 vibrational normal mode in methane is excited prior to complexation. Clear infrared-induced enhancement is observed in the mass spectrum for peaks corresponding 4u below the mass of the Au+(CH4) n=2,3 complexes corresponding, presumably, to the loss of two H2 molecules. |
| first_indexed | 2024-03-07T06:46:44Z |
| format | Journal article |
| id | oxford-uuid:fb199beb-5d8b-44ba-81db-69c89c18e4ea |
| institution | University of Oxford |
| last_indexed | 2024-03-07T06:46:44Z |
| publishDate | 2017 |
| publisher | Springer US |
| record_format | dspace |
| spelling | oxford-uuid:fb199beb-5d8b-44ba-81db-69c89c18e4ea2022-03-27T13:11:18ZInfrared spectroscopy of Au+(CH4)n complexes and vibrationally-enhanced C–H activation reactionsJournal articlehttp://purl.org/coar/resource_type/c_dcae04bcuuid:fb199beb-5d8b-44ba-81db-69c89c18e4eaSymplectic Elements at OxfordSpringer US2017Gentleman, AGreen, APrice, DCunningham, EIskra, AMackenzie, SRA combined spectroscopic and computational study of gas-phase Au+(CH4) n (n = 3–8) complexes reveals a strongly-bound linear Au+(CH4)2 core structure to which up to four additional ligands bind in a secondary coordination shell. Infrared resonance-enhanced photodissociation spectroscopy in the region of the CH4 a 1 and t 2 fundamental transitions reveals essentially free internal rotation of the core ligands about the H4C–Au+–CH4 axis, with sharp spectral features assigned by comparison with spectral simulations based on density functional theory. In separate experiments, vibrationally-enhanced dehydrogenation is observed when the t 2 vibrational normal mode in methane is excited prior to complexation. Clear infrared-induced enhancement is observed in the mass spectrum for peaks corresponding 4u below the mass of the Au+(CH4) n=2,3 complexes corresponding, presumably, to the loss of two H2 molecules. |
| spellingShingle | Gentleman, A Green, A Price, D Cunningham, E Iskra, A Mackenzie, SR Infrared spectroscopy of Au+(CH4)n complexes and vibrationally-enhanced C–H activation reactions |
| title | Infrared spectroscopy of Au+(CH4)n complexes and vibrationally-enhanced C–H activation reactions |
| title_full | Infrared spectroscopy of Au+(CH4)n complexes and vibrationally-enhanced C–H activation reactions |
| title_fullStr | Infrared spectroscopy of Au+(CH4)n complexes and vibrationally-enhanced C–H activation reactions |
| title_full_unstemmed | Infrared spectroscopy of Au+(CH4)n complexes and vibrationally-enhanced C–H activation reactions |
| title_short | Infrared spectroscopy of Au+(CH4)n complexes and vibrationally-enhanced C–H activation reactions |
| title_sort | infrared spectroscopy of au ch4 n complexes and vibrationally enhanced c h activation reactions |
| work_keys_str_mv | AT gentlemana infraredspectroscopyofauch4ncomplexesandvibrationallyenhancedchactivationreactions AT greena infraredspectroscopyofauch4ncomplexesandvibrationallyenhancedchactivationreactions AT priced infraredspectroscopyofauch4ncomplexesandvibrationallyenhancedchactivationreactions AT cunninghame infraredspectroscopyofauch4ncomplexesandvibrationallyenhancedchactivationreactions AT iskraa infraredspectroscopyofauch4ncomplexesandvibrationallyenhancedchactivationreactions AT mackenziesr infraredspectroscopyofauch4ncomplexesandvibrationallyenhancedchactivationreactions |