Multimetallic Arrays: Bi-, Tri-, Tetra-, and Hexametallic Complexes Based on Gold(I) and Gold(III) and the Surface Functionalization of Gold Nanoparticles with Transition Metals KnightEdward R. LeungNina H. ThompsonAmber L. HogarthG. D. E. T. Wilton-ElyJames 2009 Reaction of [AuCl(PPh<sub>3</sub>)] with the zwitterion S<sub>2</sub>CNC<sub>4</sub>H<sub>8</sub>NH<sub>2</sub> yields [(Ph<sub>3</sub>P)Au(S<sub>2</sub>CNC<sub>4</sub>H<sub>8</sub>NH<sub>2</sub>)]BF<sub>4</sub>. Treatment of this species with NEt<sub>3</sub> and CS<sub>2</sub> followed by [AuCl(PPh<sub>3</sub>)] leads to [{(Ph<sub>3</sub>P)Au}<sub>2</sub>(S<sub>2</sub>CNC<sub>4</sub>H<sub>8</sub>NCS<sub>2</sub>)], which can also be obtained directly from [AuCl(PPh<sub>3</sub>)] and KS<sub>2</sub>CNC<sub>4</sub>H<sub>8</sub>NCS<sub>2</sub>K. A heterobimetallic variant, [(dppm)<sub>2</sub>Ru(S<sub>2</sub>CNC<sub>4</sub>H<sub>8</sub>NCS<sub>2</sub>)Au(PPh<sub>3</sub>)]<sup>+</sup>, can be prepared by the sequential reaction of [(dppm)<sub>2</sub>Ru(S<sub>2</sub>CNC<sub>4</sub>H<sub>8</sub>NH<sub>2</sub>)]<sup>2+</sup> with NEt<sub>3</sub> and CS<sub>2</sub> followed by [AuCl(PPh<sub>3</sub>)]. Reaction of the same ruthenium precursor with [(dppm)(AuCl)<sub>2</sub>] under similar conditions yields the trimetallic complex [(dppm)<sub>2</sub>Ru(S<sub>2</sub>CNC<sub>4</sub>H<sub>8</sub>NCS<sub>2</sub>)Au<sub>2</sub>(dppm)]<sup>2+</sup>. Attempts to prepare the compound [(dppm)Au<sub>2</sub>(S<sub>2</sub>CNC<sub>4</sub>H<sub>8</sub>NH<sub>2</sub>)]<sup>2+</sup> from [(dppm)(AuCl)<sub>2</sub>] led to isolation of the known complex [{(dppm)Au<sub>2</sub>}<sub>2</sub>(S<sub>2</sub>CNC<sub>4</sub>H<sub>8</sub>NCS<sub>2</sub>)]<sup>2+</sup> via a symmetrization pathway. [{(dppf)Au<sub>2</sub>}<sub>2</sub>(S<sub>2</sub>CNC<sub>4</sub>H<sub>8</sub>NCS<sub>2</sub>)]<sup>2+</sup> was successfully prepared from [(dppf)(AuCl)<sub>2</sub>] and crystallographically characterized. In addition, a gold(III) trimetallic compound, [{(dppm)<sub>2</sub>Ru(S<sub>2</sub>CNC<sub>4</sub>H<sub>8</sub>NCS<sub>2</sub>)}<sub>2</sub>Au]<sup>3+</sup>, and a tetrametallic gold(I) species, [{(dppm)<sub>2</sub>Ru(S<sub>2</sub>CNC<sub>4</sub>H<sub>8</sub>NCS<sub>2</sub>)Au}<sub>2</sub>]<sup>2+</sup>, were also synthesized. This methodology was further exploited to attach the zwitterionic (dppm)<sub>2</sub>Ru(S<sub>2</sub>CNC<sub>4</sub>H<sub>8</sub>NCS<sub>2</sub>) unit to the surface of gold nanoparticles, which were generated in situ and found to be 3.4 (±0.3) and 14.4 (±2.5) nm in diameter depending on the method employed. Nanoparticles with a mixed surface topography were also explored.