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Abstract

The reactions of the ammonium salt of closo-decahydrodecaborate (NH₄)₂B₁₀H₁₀ with alcohols were studied in concentrated sulfuric acid medium. Alcohols ROH (R = CH₃, C₂H₅, C₃H₇, iso-C₃H₇, C₄H₉, 2-C₄H₉, ter-C₄H_9, C₅H₁₁) played the role of solvent and ligand, simultaneously. These Electrophile Induced Nucleophilic Substitution Reactions were conducted at two different temperatures (25°C or reflux) in atmospheric air and produced [2-B₁₀H₉OR]^2 −, [2,7(8)-B₁₀H₈(OR)₂]²^– and/or [B₁₀H₇(OR)₃]²^–. The rate of the reaction and the nature of the product formed depended on the temperature, on the alcohol, and on the reaction duration. The reactions at 25°C, if proceeded, produced mainly the monoalkoxy derivative, [2-B₁₀H₉OR]²^–. For the longer chain alcohols (4 carbons and above) the increase in the reaction duration and the temperature resulted in higher substitution, thus producing the dialkoxy [2,7(8)-B₁₀H₈(OR)₂]²^– and trialkoxy [B₁₀H₇(OR)₃]²^– derivatives. Meanwhile only the monoalkoxy [2-B₁₀H₉OR]²^– plus the dialkyloxonium [2-B₁₀H₉OR₂]⁻ derivatives were produced with the shorter alcohols (1 to 3 carbons) at refluxing temperature. All these derivatives were isolated in their pure forms on DEAE-cellulose column with adequate yields, and characterized by ¹¹B, ¹³C, ¹H NMR, negative ESI and TLC.

Keywords

Decahydrodecaborate boron hydride boron compound alkoxy derivatives

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Study of the controlled temperature reaction between closo -decahydrodecaborate and alcohols in H 2 SO 4 medium

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