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A High Yield Synthesis of an Octastannacubane and a Bis(silyl) Stannylene via Reductive Elimination of a Silane
Author(s) -
Bashkurov Roman,
Kratish Yosi,
Fridman Natalia,
BravoZhivotovskii Dmitry,
Apeloig Yitzhak
Publication year - 2021
Publication title -
angewandte chemie
Language(s) - English
Resource type - Journals
eISSN - 1521-3757
pISSN - 0044-8249
DOI - 10.1002/ange.202013007
Subject(s) - silylation , chemistry , yield (engineering) , silane , reductive elimination , thermal decomposition , tin , hydride , medicinal chemistry , nuclear magnetic resonance spectroscopy , molecule , decomposition , stereochemistry , crystallography , organic chemistry , metal , catalysis , materials science , metallurgy
Thermolysis of tris(silyl) tin hydride 2 at 70 °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 NHC Me yielding stannylene‐NHC Me complex 5 . Upon heating (70 °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 °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.