Journal
ANGEWANDTE CHEMIE-INTERNATIONAL EDITION
Volume 60, Issue 6, Pages 2898-2902Publisher
WILEY-V C H VERLAG GMBH
DOI: 10.1002/anie.202013007
Keywords
cluster compounds; cubanes; low-valent tin compounds; stannylenes; tin
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Funding
- Israel Science Foundation (ISF)
- Alexander Goldberg research fund at the Technion
- Ministry of Immigrant Absorption, State of Israel
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Thermolysis of tris(silyl) tin hydride 2 at 70 degrees C for 3 hours leads to the formation of various silyl-stannylene compounds, including the novel octastannacubane 9; the mechanism of this reaction mainly involves elimination reactions and dimerization reactions.
Thermolysis of tris(silyl) tin hydride 2 at 70 degrees C for 3 hours results in elimination of tBu(2)MeSiH 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 degrees C, 24 h) 4 yields stannyl radical 8 along with pentastannatricyclo[2.1.0.0(2, 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 degrees C) of 1,1,2,2-tetrasilyldistannane 11, along with tBu(2)MeSiH. 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 tBu(2)MeSiH molecules from 11 yielding a distannyne, (or its bis-stannylene isomer), followed by its tetramerization.
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