Gold(I) Phosphine/Phosphido‐Borohydride Complexes

A homologous series of linear, mononuclear gold(I) phosphine/phosphido‐borohydride complexes, encompassing [Au(PR 3 ) 2 ] + 1 , [Au(PR 3 )(PR 2 BH 3 )] 2 and [Au(PR 2 BH 3 ) 2 ] – 3 (R = t Bu, Ad), has been prepared and structurally characterized. Strong intramolecular dispersion interactions are evident in the complexes with Ad‐substituted ligands, which adopt eclipsed conformations in the solid state exclusively while there is no clear preference for the t Bu‐substituted analogues. Despite the disparate donor properties of the phosphine and phosphido‐borohydride ligands, there are no statistically significant differences in Au–P bond length (≈2.33 Å) across the series. This difference is, however, manifested in the redox characteristics of the gold(I) complexes, which are more readily oxidized in the order 1 < 2 < 3 .