A High Yield Synthesis of an Octastannacubane and a Bis(silyl) Stannylene via Reductive Elimination of a Silane

Roman Bashkurov, Yosi Kratish, Natalia Fridman, Dmitry Bravo-Zhivotovskii*, Yitzhak Apeloig

*Corresponding author for this work

Research output: Contribution to journalArticlepeer-review

14 Scopus citations

Abstract

Thermolysis of tris(silyl) tin hydride 2 at 70 °C for 3 hours results in elimination of tBu2MeSiH and generation of bis(silyl) stannylene 3 which dimerizes instantaneously yielding distannene 4. Compound 3 can be trapped by NHCMe yielding stannylene-NHCMe complex 5. Upon heating (70 °C, 24 h) 4 yields stannyl radical 8 along with pentastannatricyclo[2.1.0.02, 5]pentane 10 (ca. 30 %) and traces (ca. 5 %) of the novel octastannacubane 9. Remarkably, octastannacubane 9 is produced in 70 % yield by mild heating (50 °C) of 1,1,2,2-tetrasilyldistannane 11, along with tBu2MeSiH. Octastannacubane 9 was characterized by X-ray crystallography, NMR and UV/Vis spectroscopy. Based on DFT quantum-mechanical calculations the 11 → 9 transformation occurs via reductive elimination of two tBu2MeSiH molecules from 11 yielding a distannyne, (or its bis-stannylene isomer), followed by its tetramerization.

Original languageEnglish (US)
Pages (from-to)2898-2902
Number of pages5
JournalAngewandte Chemie - International Edition
Volume60
Issue number6
DOIs
StatePublished - Feb 8 2021

Funding

This research was supported by the Israel Science Foundation (ISF) and by the Alexander Goldberg research fund at the Technion. D.B.‐Z. is grateful to the Ministry of Immigrant Absorption, State of Israel, for a Kamea fellowship.

Keywords

  • cluster compounds
  • cubanes
  • low-valent tin compounds
  • stannylenes
  • tin

ASJC Scopus subject areas

  • Catalysis
  • General Chemistry

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