A High Yield Synthesis of an Octastannacubane and a Bis(silyl) Stannylene via Reductive Elimination of a Silane.
cluster compounds
cubanes
low-valent tin compounds
stannylenes
tin
Journal
Angewandte Chemie (International ed. in English)
ISSN: 1521-3773
Titre abrégé: Angew Chem Int Ed Engl
Pays: Germany
ID NLM: 0370543
Informations de publication
Date de publication:
08 Feb 2021
08 Feb 2021
Historique:
received:
25
09
2020
pubmed:
4
11
2020
medline:
4
11
2020
entrez:
3
11
2020
Statut:
ppublish
Résumé
Thermolysis of tris(silyl) tin hydride 2 at 70 °C for 3 hours results in elimination of tBu
Identifiants
pubmed: 33142030
doi: 10.1002/anie.202013007
doi:
Types de publication
Journal Article
Langues
eng
Sous-ensembles de citation
IM
Pagination
2898-2902Subventions
Organisme : This research was supported by the Israel Science Foundation (ISF) and by the Alexander Goldberg research fund at the Technion.
Informations de copyright
© 2020 Wiley-VCH GmbH.
Références
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All calculations were done using Gaussian 09 Rev. D1 software. All calculations were performed using Density Functional Theory using the B3PW91-D3/6-311+G(d,p) [H, C, Si], SDD [Sn]//B3PW91-D3/6-31G(d,p) [H, C, Si], SDD [Sn] level of theory; further computational details and a full reference list for the methods used are provided in the SI.
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IUPAC name, octakis(di-tert-butyl(methyl)silyl)pentacyclo [4.2.0.02,5.03,8.04,7]octastannacubane.
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Disappointingly, we were unable to measure the expected 2J(119Sn-117Sn) and 3J(119Sn-117Sn) coupling constants; probably the 2J coupling constants are poorly resolved and the value of 3J is smaller than the line width of the parent peak (w1/2=67 Hz).
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The calculations also show that the 1,1-silane elimination pathway is preferred over the 1,2-silane elimination route. The alternative 1,2-elimination, to give a distannene followed by 1,2-elimination of a second silane molecule also yielding distannyne intermediates 13′ or 14′, have similar thermodynamic energies to the 1,1-elimination route (see SI). However, the activation barrier for the 1,2-Me3SiH elimination from 11′ (ΔG≠=46.4 kcal mol−1; ΔH≠=46.1 kcal mol−1; TΔS≠=−0.3 kcal mol−1) is significantly higher than for the 1,1-elimination, ruling out this competing pathway.