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Characterization of hydrogen-substituted silylium ions in the condensed phase
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Characterization of hydrogen-substituted silylium ions in the condensed phase
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Characterization of hydrogen-substituted silylium ions in the condensed phase
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Journal Article
Characterization of hydrogen-substituted silylium ions in the condensed phase
2019
Overview
Hydrogen-substituted silylium ions are long-sought reactive species. We report a protolysis strategy that chemoselectively cleaves either an Si–C(sp²) or an Si–H bond using a carborane acid to access the full series of [CHB11H₅Br₆]⁻-stabilized R₂SiH⁺, RSiH₂⁺, and SiH₃⁺ cations, where bulky tert-butyl groups at the silicon atom (R = tBu) were crucial to avoid substituent redistribution.The crystallographically characterized molecular structures of [CHB11H₅Br₆]⁻-stabilized tBu₂HSi⁺ and tBuH₂Si⁺ feature pyramidalization at the silicon atom, in accordance with that of tBu₃Si⁺[CHB11H₅Br₆]⁻. Conversely, the silicon atom in the H₃Si⁺ cation adopts a trigonal-planar structure and is stabilized by two counteranions. This solid-state structure resembles that of the corresponding Brønsted acid.
Publisher
American Association for the Advancement of Science,The American Association for the Advancement of Science
Subject
