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Octahydrotriborate

Octahydrotriborate is the boron hydride anion B<sub>3</sub>H<sub>8</sub><sup>−</sup>. It forms a variety of salts that are colorless and air-stable. The tetrabutylammonium salt is soluble in organic solvents such as acetonitrile and methylene chloride. The anion is an intermediate is the synthesis of various higher boron hydrides, such as pentaborane(9). B<sub>3</sub>H<sub>8</sub><sup>−</sup> can be viewed as the conjugate base of triborane B<sub>3</sub>H<sub>9</sub>.

Preparation

Octahydrotriborate is prepared by partial oxidation of borohydride with iodine or boron trifluoride:

3BH<sub>4</sub><sup>−</sup> + I<sub>2</sub> → B<sub>3</sub>H<sub>8</sub><sup>−</sup> + 2H<sub>2</sub> + 2I<sup>−</sup>
5BH<sub>4</sub><sup>−</sup> + 4BF<sub>3</sub>O(C<sub>2</sub>H<sub>5</sub>)<sub>2</sub> → 2B<sub>3</sub>H<sub>8</sub><sup>−</sup> + 2H<sub>2</sub> + 4O(C<sub>2</sub>H<sub>5</sub>)<sub>2</sub> + 3BF<sub>4</sub><sup>−</sup>

Structure and reactions

As shown by X-ray crystallography of various salts, B<sub>3</sub>H<sub>8</sub><sup>−</sup> consists of a distorted triangle of three BH<sub>2</sub> vertices. Two edges of the triangle are occupied by bridging hydrides.

It is converted to the bromide B<sub>3</sub>H<sub>7</sub>Br<sup>−</sup> using HBr (illustrating its hydridic character):

B<sub>3</sub>H<sub>8</sub><sup>−</sup> + HBr → B<sub>3</sub>H<sub>7</sub>Br<sup>−</sup> + H<sub>2</sub>

Pyrolysis of this bromide gives pentaborane(9).

5 B<sub>3</sub>H<sub>7</sub>Br<sup>−</sup> → 3 B<sub>5</sub>H<sub>9</sub> + 5 Br<sup>−</sup> + 4 H<sub>2</sub>

Also consistent with its basicity, B<sub>3</sub>H<sub>8</sub><sup>_</sup> functions as a bidentate ligand in a variety of coordination complexes, e.g. Cr(B<sub>3</sub>H<sub>8</sub>)<sub>2</sub>.

References