Infrared spectroscopy of closed s-shell gas-phase M+(N2O)n (M = Li, Al) ion-molecule complexes
We present the results of a combined experimental and computational study of the structures of gas-phase M + (N 2 O) n (M = Li, Al) complexes. Infrared spectra were recorded in the region of the N 2 O asymmetric (N = N) stretch using photodissociation spectroscopy employing the inert messenger techn...
| Main Authors: | , , , |
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| Format: | Journal article |
| Language: | English |
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Taylor and Francis
2019
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| _version_ | 1797051766514122752 |
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| author | Cunningham, E Gentleman, A Beardsmore, PW Mackenzie, S |
| author_facet | Cunningham, E Gentleman, A Beardsmore, PW Mackenzie, S |
| author_sort | Cunningham, E |
| collection | OXFORD |
| description | We present the results of a combined experimental and computational study of the structures of gas-phase M + (N 2 O) n (M = Li, Al) complexes. Infrared spectra were recorded in the region of the N 2 O asymmetric (N = N) stretch using photodissociation spectroscopy employing the inert messenger technique. Unlike in our previous studies on M + (N 2 O) n (M = Cu, Ag, Au and M = Co, Rh, Ir) complexes, N– and O–bound isomers in this case are near isoenergetic and are not distinguished spectroscopically at this resolution. In the case of Li + complexes, there is, however, evidence for the presence of bound N 2 moieties, indicating the presence of inserted, OLi + N 2 (N 2 O) n –type structures. The weak N 2 band lies to the blue of the signature of molecularly N– and O–bound ligands and is well–reproduced in the simulated spectra of energetically low-lying structures computed from density functional theory. No such inserted isomers are observed in the case of Al + (N 2 O) n complexes whose infrared spectra can be understood on the basis of molecularly-bound N 2 O ligands. The differences in M + (N 2 O) n structures observed for these closed–shell, ns 2 , metal centres relative to other metal cations are discussed in terms of the likely bonding motifs. |
| first_indexed | 2024-03-06T18:24:06Z |
| format | Journal article |
| id | oxford-uuid:07558b60-7c31-4e8f-ba62-91c08f717b42 |
| institution | University of Oxford |
| language | English |
| last_indexed | 2024-03-06T18:24:06Z |
| publishDate | 2019 |
| publisher | Taylor and Francis |
| record_format | dspace |
| spelling | oxford-uuid:07558b60-7c31-4e8f-ba62-91c08f717b422022-03-26T09:07:00ZInfrared spectroscopy of closed s-shell gas-phase M+(N2O)n (M = Li, Al) ion-molecule complexesJournal articlehttp://purl.org/coar/resource_type/c_dcae04bcuuid:07558b60-7c31-4e8f-ba62-91c08f717b42EnglishSymplectic Elements at OxfordTaylor and Francis2019Cunningham, EGentleman, ABeardsmore, PWMackenzie, SWe present the results of a combined experimental and computational study of the structures of gas-phase M + (N 2 O) n (M = Li, Al) complexes. Infrared spectra were recorded in the region of the N 2 O asymmetric (N = N) stretch using photodissociation spectroscopy employing the inert messenger technique. Unlike in our previous studies on M + (N 2 O) n (M = Cu, Ag, Au and M = Co, Rh, Ir) complexes, N– and O–bound isomers in this case are near isoenergetic and are not distinguished spectroscopically at this resolution. In the case of Li + complexes, there is, however, evidence for the presence of bound N 2 moieties, indicating the presence of inserted, OLi + N 2 (N 2 O) n –type structures. The weak N 2 band lies to the blue of the signature of molecularly N– and O–bound ligands and is well–reproduced in the simulated spectra of energetically low-lying structures computed from density functional theory. No such inserted isomers are observed in the case of Al + (N 2 O) n complexes whose infrared spectra can be understood on the basis of molecularly-bound N 2 O ligands. The differences in M + (N 2 O) n structures observed for these closed–shell, ns 2 , metal centres relative to other metal cations are discussed in terms of the likely bonding motifs. |
| spellingShingle | Cunningham, E Gentleman, A Beardsmore, PW Mackenzie, S Infrared spectroscopy of closed s-shell gas-phase M+(N2O)n (M = Li, Al) ion-molecule complexes |
| title | Infrared spectroscopy of closed s-shell gas-phase M+(N2O)n (M = Li, Al) ion-molecule complexes |
| title_full | Infrared spectroscopy of closed s-shell gas-phase M+(N2O)n (M = Li, Al) ion-molecule complexes |
| title_fullStr | Infrared spectroscopy of closed s-shell gas-phase M+(N2O)n (M = Li, Al) ion-molecule complexes |
| title_full_unstemmed | Infrared spectroscopy of closed s-shell gas-phase M+(N2O)n (M = Li, Al) ion-molecule complexes |
| title_short | Infrared spectroscopy of closed s-shell gas-phase M+(N2O)n (M = Li, Al) ion-molecule complexes |
| title_sort | infrared spectroscopy of closed s shell gas phase m n2o n m li al ion molecule complexes |
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