| Téléchargement | - Voir la version finale : Chlorine-35 solid-state nuclear magnetic resonance spectroscopy as an indirect probe of the oxidation number of tin in tin chlorides (PDF, 3.1 Mio)
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| DOI | Trouver le DOI : https://doi.org/10.1021/acs.inorgchem.0c02025 |
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| Auteur | Rechercher : Lucier, Bryan E. G.Identifiant ORCID : https://orcid.org/0000-0002-9682-4324; Rechercher : Terskikh, Victor V.1Identifiant ORCID : https://orcid.org/0000-0003-1514-2610; Rechercher : Guo, Jiacheng; Rechercher : Bourque, Jeremy L.; Rechercher : Mconie, Sarah L.; Rechercher : Ripmeester, John A.2Identifiant ORCID : https://orcid.org/0000-0002-4091-5120; Rechercher : Huang, YiningIdentifiant ORCID : https://orcid.org/0000-0001-9265-5896; Rechercher : Baines, Kim M.Identifiant ORCID : https://orcid.org/0000-0001-6515-5749 |
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| Affiliation | - Conseil national de recherches du Canada. Centre de recherche en métrologie
- Conseil national de recherches du Canada. Technologies de sécurité et de rupture
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| Format | Texte, Article |
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| Sujet | granular materials; platinum; anions; oxidation; nuclear magnetic resonance spectroscopy |
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| Résumé | Ultrawideline ³⁵Cl solid-state nuclear magnetic resonance (SSNMR) spectra of a series of 12 tin chlorides were recorded. The magnitude of the ³⁵Cl quadrupolar coupling constant (CQ) was shown to consistently indicate the chemical state (oxidation number) of the bound Sn center. The chemical state of the Sn center was independently verified by tin Mössbauer spectroscopy. CQ(³⁵Cl) values of >30 MHz correspond to Sn(IV), while CQ(³⁵Cl) readings of <30 MHz indicate that Sn(II) is present. Tin-119 SSNMR experiments would seem to be the most direct and effective route to interrogating tin in these systems, yet we show that ambiguous results can emerge from this method, which may lead to an incorrect interpretation of the Sn oxidation number. The accumulated ³⁵Cl NMR data are used as a guide to assign the Sn oxidation number in the mixed-valent metal complex Ph₃PPdᴵᵐSnCl₂. The synthesis and crystal structure of the related Ph₃PPtᴵᵐSnCl₂ are reported, and ¹⁹⁵Pt and ³⁵Cl SSNMR experiments were also used to investigate its Pt–Sn bonding. Plane-wave DFT calculations of ³⁵Cl, ¹¹⁹Sn, and ¹⁹⁵Pt NMR parameters are used to model and interpret experimental data, supported by computed ¹¹⁹Sn and ¹⁹⁵Pt chemical shift tensor orientations. Given the ubiquity of directly bound Cl centers in organometallic and inorganic systems, there is tremendous potential for widespread usage of ³⁵Cl SSNMR parameters to provide a reliable indication of the chemical state in metal chlorides. |
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| Date de publication | 2020-09-21 |
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| Maison d’édition | American Chemical Society |
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| Licence | |
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| Dans | |
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| Langue | anglais |
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| Publications évaluées par des pairs | Oui |
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| Exporter la notice | Exporter en format RIS |
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| Signaler une correction | Signaler une correction (s'ouvre dans un nouvel onglet) |
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| Identificateur de l’enregistrement | 98a03cf7-806d-4637-9ed1-0d108204e564 |
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| Enregistrement créé | 2021-05-11 |
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| Enregistrement modifié | 2021-05-12 |
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