Reactions of  Sn(Si( Bu)2Me)3 with HM(CO)3C5R5 (M = Cr or Mo, R = H or CH3) and Hg. Ionic, covalent, and μ-CO bonding patterns between transition metals and tin

Koppaka, Anjaneyulu; Cai, Xiaojun; Majumdar, Shikharesh; Etezadi, Sedigheh; Serafim, Leonardo F.; Temprado, Manuel; Captain, Burjor; Hoff, Carl D.

doi:10.1016/j.ica.2017.09.052

“…Thermolysis at 70 8C for 3 hours of branched tris(silyl) tin hydride 2 [14] in hexane solution produces a green colored solution. According to 29 Si NMR spectroscopy 2 is quantitatively converted to distannene 4 [15] and tBu 2 MeSiH (Scheme 2).…”

mentioning

confidence: 99%

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

Bashkurov

¹

,

Kratish

²

,

Fridman

³

et al. 2020

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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.

show abstract

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

Bashkurov

¹

,

Kratish

²

,

Fridman

³

et al. 2020

View full text Add to dashboard Cite

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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