The products of the reaction between <i>N</i>,<i>N</i>′-diphosphanylimidazol-2-ylidene
(<b>P–C–P</b>) and gold(I) precursors depend on
the nature of the anions associated with the latter. In contrast to
the reported reaction with [Au(tht)<sub>2</sub>(OTf)], the use of
[AuCl(tht)] led to the new hexanuclear complex <b>1</b>, which
features a Au<sub>6</sub>(μ<sub>3</sub>-<b>P–C</b>,κ<i>C</i>,κ<i>N</i>,κ<i>P</i>)<sub>3</sub> skeleton. The reaction of lithium imidazolide
(<b>P–C–Li</b>) and [AuCl(tht)] also afforded <b>1</b>, together with an unusual salt of the general formula [Au<sub>5</sub>Cl(μ<sub>3</sub>-<b>P–C</b>-κ<i>P</i>,κ<i>C</i>,κ<i>N</i>)<sub>3</sub>]<sub>2</sub>[AuCl<sub>2</sub>]<sub>2</sub> (<b>2</b>), which contains [Au<sub>5</sub>(μ<sub>3</sub>-<b>P–C</b>-κ<i>P</i>,κ<i>C</i>,κ<i>N</i>)]<sup>+</sup> subunits. In the solid state, one of these
Au<sub>5</sub> cations is associated with an [AuCl<sub>2</sub>]<sup>−</sup> anion, while two other cations interact through their
unique dicoordinated N–Au–N center with a [AuCl<sub>2</sub>]<sup>−</sup> anion, with the charge of the resulting
monocation being compensated for by another [AuCl<sub>2</sub>]<sup>−</sup> anion to give a Au<sub>12</sub> salt. Remarkably,
the latter displays seven different bonding types at Au<sup>I</sup>: C–Au–C, N–Au–N, P–Au–P,
Cl–Au–Cl, C–Au–N, P–Au–Cl,
and Au···Au
