Exceptionally large “through-space” nuclear spin coupling in a 2,4,6-tri(phosphanyl)–1,3,5- triphosphabenzene
We describe the synthesis of a phosphanyl-functionalized 1,3,5-triphosphabenzene that exhibits remarkably large indirect spin–spin coupling (432 Hz) between phosphorus-31 nuclei. The magnitude of this coupling interaction is indicative of highly effective orbital overlap between two lone-pair type o...
| Authors: | , , , , , , |
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| Format: | article |
| Publication Date: | 2025 |
| Country: | España |
| Institution: | Universidad Complutense de Madrid (UCM) |
| Repository: | Docta Complutense |
| Language: | English |
| OAI Identifier: | oai:docta.ucm.es:20.500.14352/133452 |
| Online Access: | https://hdl.handle.net/20.500.14352/133452 |
| Access Level: | Open access |
| Keyword: | 547 Química 23 Química |
| Summary: | We describe the synthesis of a phosphanyl-functionalized 1,3,5-triphosphabenzene that exhibits remarkably large indirect spin–spin coupling (432 Hz) between phosphorus-31 nuclei. The magnitude of this coupling interaction is indicative of highly effective orbital overlap between two lone-pair type orbitals, each of which possesses significant s-orbital character. This was probed computationally using density functional theory calculations in order to deconvolute individual transmission pathways by dividing these into “through-space” and “through-bond” type interactions. The “through-space” transmission pathway can be chemically disrupted by oxidation of the pendant phosphanyl groups using either elemental sulfur or selenium. By engaging the phosphanyl s-orbitals in bonds to the chalcogen elements, the indirect interaction is perturbed, and the NMR spectra of the resulting compounds exhibit conventional “through-bond” coupling. |
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