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Abstract

Decaborane(14) reacts with NaNO₂ in tetrahydrofuran forming the [9-tetrahydrofuran-6-NO₂B₁₀H₁₂]^- salt which after protonization with concentrated H₂SO₄ or diluted HCl affords azaboranes 6-NB₉H₁₂ and 4-NB₈H₁₃, respectively. The 6-NB₉H₁₂ azaborane is hydrolyzed to the 4-NB₈H₁₃ azaborane and reacts with Lewis bases under the formation of the 9-L-6-NB₉H₁₂ ligand derivatives (L = (CH)S, CHCN, (CH)P). By the reduction of 9-CHCN-6-NBH with LiAlH₄ in tetrahydrofuran the 6-NB₉H₁₃^- anion was prepared. By an analogous reaction of decaborane(14) with KHSO₃ in water and by a subsequent protonization of the formed intermediate with concentrated H₂SO₄ or diluted HCl the thiaboranes 6-SB₉H₁₁ and 4-SB₈H₁₂, respectively, were prepared. The reaction of decaborane(14) with Na₂SeO₃ in tetrahydrofuran followed by the protonization of the intermediate with diluted HCl afforded the 7,8-Se₂B₉H₉ species. Structures of all compounds were proposed on the basis of the ¹¹B and ¹H NMR spectra; in the case of 4-NB₈H₁₃, the structure was determined by the X-ray diffraction analysis.