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1‐Oxa‐nido‐dodecaborate [OB11H12]− from the Controlled Oxidation of the closo‐Borates [B11H11]2− and [B12H12]2−
Authors:Oleg Volkov  Peter Paetzold  Chunhua Hu
Abstract:The closo‐dodecaborate [B12H12]2? is degraded at room temperature by oxygen in an acidic aqueous solution in the course of several weeks to give B(OH)3. The degradation is induced by Ag2+ ions, generated from Ag+ by the action of H2S2O8. Oxa‐nido‐dodecaborate(1?) is an intermediate anion, that can be separated from the reaction mixture as [NBzlEt3][OB11H12] after five days in a yield of 18 %. The action of FeCl3 on the closo‐undecaborate [B11H11]2? in an aqueous solution gives either [B22H22]2? (by fusion) or nido‐B11H13(OH)? (by protonation and hydration), depending on the concentration of FeCl3. In acetonitrile, however, [B11H11]2? is transformed into [OB11H12]? by Fe3+ and oxygen. The radical anions [B12H12] ˙ ? and [B11H11] ˙ ? are assumed to be the primary products of the oxidation with the one‐electron oxidants Ag2+ and Fe3+, respectively. These radical anions are subsequently transformed into [OB11H12]? by oxygen. The crystal structure analysis shows that the structure of [OB11H12]? is derived from the hypothetical closo‐oxaborane OB12H12 by removal of the B3 vertex, leaving a non‐planar pentagonal aperture with a three‐coordinate O vertex, as predicted by NMR spectra and theory.
Keywords:Undecahydroundecaborate(2−  )  Dodecahydrododecaborate(2−  )  Dodecahydrooxadodecaborate(1−  )  Oxidative Cluster Degradation  Crystal Structure
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