Investigating unusual homonuclear intermolecular “through-space” J couplings in organochalcogen systems
<p>Although the electron-mediated spin–spin or J coupling is conventionally viewed as transmitted via covalent bonds, examples of J couplings between atoms that are not formally bonded but are in close proximity (termed “through-space” J couplings) have been reported. In this work, we investig...
| Main Authors: | , , , , , , , , , |
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| Format: | Journal article |
| Language: | English |
| Published: |
American Chemical Society
2016
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| _version_ | 1826295633163583488 |
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| author | Camacho, P McKay, D Dawson, DM Kirst, C Yates, JR Green, TFG Cordes, DB Slawin, AMZ Woollins, JD Ashbrook, SE |
| author_facet | Camacho, P McKay, D Dawson, DM Kirst, C Yates, JR Green, TFG Cordes, DB Slawin, AMZ Woollins, JD Ashbrook, SE |
| author_sort | Camacho, P |
| collection | OXFORD |
| description | <p>Although the electron-mediated spin–spin or J coupling is conventionally viewed as transmitted via covalent bonds, examples of J couplings between atoms that are not formally bonded but are in close proximity (termed “through-space” J couplings) have been reported. In this work, we investigate the observation of homonuclear <sup>31</sup>P J couplings in organochalcogen heterocycles, which occur between <sup>31</sup>P in two separate molecules, confirming without doubt their through-space nature. The presence of this interaction is even more surprising for one compound, where it occurs between crystallographically equivalent species. Although crystallographically equivalent species need not be magnetically equivalent in the solid state, owing to the presence of anisotropic interactions, we demonstrate that it is not the shielding anisotropy that lifts magnetic equivalence, in this case, but the presence of heteronuclear couplings to <sup>77</sup>Se. We support our experimental observations with periodic scalar-relativistic density functional theory calculations and coupling density deformation plots to visualize the mechanism of these interesting interactions.</p> |
| first_indexed | 2024-03-07T04:04:03Z |
| format | Journal article |
| id | oxford-uuid:c58a9436-9bd6-4d03-bc2f-ad1883ece0ba |
| institution | University of Oxford |
| language | English |
| last_indexed | 2024-03-07T04:04:03Z |
| publishDate | 2016 |
| publisher | American Chemical Society |
| record_format | dspace |
| spelling | oxford-uuid:c58a9436-9bd6-4d03-bc2f-ad1883ece0ba2022-03-27T06:31:45ZInvestigating unusual homonuclear intermolecular “through-space” J couplings in organochalcogen systemsJournal articlehttp://purl.org/coar/resource_type/c_dcae04bcuuid:c58a9436-9bd6-4d03-bc2f-ad1883ece0baEnglishSymplectic Elements at OxfordAmerican Chemical Society2016Camacho, PMcKay, DDawson, DMKirst, CYates, JRGreen, TFGCordes, DBSlawin, AMZWoollins, JDAshbrook, SE<p>Although the electron-mediated spin–spin or J coupling is conventionally viewed as transmitted via covalent bonds, examples of J couplings between atoms that are not formally bonded but are in close proximity (termed “through-space” J couplings) have been reported. In this work, we investigate the observation of homonuclear <sup>31</sup>P J couplings in organochalcogen heterocycles, which occur between <sup>31</sup>P in two separate molecules, confirming without doubt their through-space nature. The presence of this interaction is even more surprising for one compound, where it occurs between crystallographically equivalent species. Although crystallographically equivalent species need not be magnetically equivalent in the solid state, owing to the presence of anisotropic interactions, we demonstrate that it is not the shielding anisotropy that lifts magnetic equivalence, in this case, but the presence of heteronuclear couplings to <sup>77</sup>Se. We support our experimental observations with periodic scalar-relativistic density functional theory calculations and coupling density deformation plots to visualize the mechanism of these interesting interactions.</p> |
| spellingShingle | Camacho, P McKay, D Dawson, DM Kirst, C Yates, JR Green, TFG Cordes, DB Slawin, AMZ Woollins, JD Ashbrook, SE Investigating unusual homonuclear intermolecular “through-space” J couplings in organochalcogen systems |
| title | Investigating unusual homonuclear intermolecular “through-space” J couplings in organochalcogen systems |
| title_full | Investigating unusual homonuclear intermolecular “through-space” J couplings in organochalcogen systems |
| title_fullStr | Investigating unusual homonuclear intermolecular “through-space” J couplings in organochalcogen systems |
| title_full_unstemmed | Investigating unusual homonuclear intermolecular “through-space” J couplings in organochalcogen systems |
| title_short | Investigating unusual homonuclear intermolecular “through-space” J couplings in organochalcogen systems |
| title_sort | investigating unusual homonuclear intermolecular through space j couplings in organochalcogen systems |
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