| Summary: | Gold(III) complexation with the octadecahydrido-eicosaborate anion [B<sub>20</sub>H<sub>18</sub>]<sup>2−</sup> was studied for the first time. It was found that when gold(III) complexes [Au(L)Cl<sub>2</sub>]BF<sub>4</sub> (L = bipy, phen) reacted with [B<sub>20</sub>H<sub>18</sub>]<sup>2−</sup>, complexes [Au(L)Cl<sub>2</sub>]<sub>2</sub>[B<sub>20</sub>H<sub>18</sub>] were isolated. The compounds consisted of a cationic gold(III) complex [Au(L)Cl<sub>2</sub>]<sup>+</sup> and the hydridoborate cluster as a counterion. X-ray diffraction studies revealed weak B–H...Au interactions for both compounds. Note that more reactive anions [B<i><sub>n</sub></i>H<i><sub>n</sub></i>]<sup>2−</sup> (<i>n</i> = 10, 12) in similar reactions with gold(III) complexes resulted in gold mirror reactions.
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