TY - JOUR
T1 - A High Yield Synthesis of an Octastannacubane and a Bis(silyl) Stannylene via Reductive Elimination of a Silane
AU - Bashkurov, Roman
AU - Kratish, Yosi
AU - Fridman, Natalia
AU - Bravo-Zhivotovskii, Dmitry
AU - Apeloig, Yitzhak
N1 - Funding Information:
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.
Publisher Copyright:
© 2020 Wiley-VCH GmbH
PY - 2021/2/8
Y1 - 2021/2/8
N2 - 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.
AB - 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.
KW - cluster compounds
KW - cubanes
KW - low-valent tin compounds
KW - stannylenes
KW - tin
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U2 - 10.1002/anie.202013007
DO - 10.1002/anie.202013007
M3 - Article
C2 - 33142030
AN - SCOPUS:85097446008
VL - 60
SP - 2898
EP - 2902
JO - Angewandte Chemie - International Edition
JF - Angewandte Chemie - International Edition
SN - 1433-7851
IS - 6
ER -