A High Yield Synthesis of an Octastannacubane and a Bis(silyl) Stannylene via Reductive Elimination of a Silane. Issue 6 (10th December 2020)

• Record Type: Journal Article
• Authors: Bashkurov, Roman; Kratish, Yosi; Fridman, Natalia; Bravo‐Zhivotovskii, Dmitry; Apeloig, Yitzhak
• Is Part Of: Angewandte Chemie international edition. Volume 60:Issue 6(2021)
• Page Start: 2898
• Page End: 2902
• Publication Date: 2020-12-10
• Subjects: cluster compounds -- cubanes -- low-valent tin compounds -- stannylenes -- tin; Chemistry -- Periodicals; 540
• DOI: 10.1002/anie.202013007
• Languages: English
• ISSNs: 1433-7851

Abstract

Abstract: Thermolysis of tris(silyl) tin hydride 2 at 70 °C for 3 hours results in elimination of tBu2 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 tBu2 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 tBu2 MeSiH molecules from 11 yielding a distannyne, (or its bis‐stannylene isomer), followed by its tetramerization. Abstract : A high yield synthesis (70 %) of a novel octastannacubane 2 under mild conditions (50 °C) involves reductive elimination of two silane molecules from a 1, 1, 2, 2‐tetrasilyldistannane 1 followed by tetramerization. A mechanism for the 1 →2 transformation is proposed by DFT calculations.