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

doi:10.1002/anie.202013007

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

Chemistry

Research output: Contribution to journal › Article › peer-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 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 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 language	English (US)
Pages (from-to)	2898-2902
Number of pages	5
Journal	Angewandte Chemie - International Edition
Volume	60
Issue number	6
DOIs	https://doi.org/10.1002/anie.202013007
State	Published - 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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10.1002/anie.202013007

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

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.",

keywords = "cluster compounds, cubanes, low-valent tin compounds, stannylenes, tin",

author = "Roman Bashkurov and Yosi Kratish and Natalia Fridman and Dmitry Bravo-Zhivotovskii and Yitzhak Apeloig",

note = "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: {\textcopyright} 2020 Wiley-VCH GmbH",

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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

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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.

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KW - cluster compounds

KW - cubanes

KW - low-valent tin compounds

KW - stannylenes

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

Abstract

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Keywords

ASJC Scopus subject areas

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