Interpolymetallic Assembly of d<sup>8</sup>−d<sup>10</sup> Sulfide Aggregates from [Pt<sub>2</sub>(PPh<sub>3</sub>)<sub>4</sub>(μ-S)<sub>2</sub>] and Group 12 Metals

A series of heterometallic Pt−M (M = Zn and Cd) sulfide aggregates with growing nuclearities {Pt<sub>2</sub>M}, {Pt<sub>4</sub>M}, and {Pt<sub>4</sub>M<sub>2</sub>}, viz., [ZnPt<sub>2</sub>Cl<sub>2</sub>(PPh<sub>3</sub>)<sub>4</sub>(μ<sub>3</sub>-S)<sub>2</sub>] (<b>2</b>), [CdPt<sub>2</sub>Cl<sub>2</sub>(PPh<sub>3</sub>)<sub>4</sub>(μ<sub>3</sub>-S)<sub>2</sub>] (<b>3</b>), [Pt<sub>2</sub>(PPh<sub>3</sub>)<sub>4</sub>(μ<sub>3</sub>-S)<sub>2</sub>]<sub>2</sub>[ZnSO<sub>4</sub>]<sub>2</sub> (<b>4</b>), [Pt<sub>2</sub>(PPh<sub>3</sub>)<sub>4</sub>(μ<sub>3</sub>-S)<sub>2</sub>]<sub>2</sub>[CdSO<sub>4</sub>]<sub>2</sub>·H<sub>2</sub>O (<b>5</b>), [CdPt<sub>4</sub>(PPh<sub>3</sub>)<sub>8</sub>(μ<sub>3</sub>-S)<sub>4</sub>][ClO<sub>4</sub>]<sub>2</sub> (<b>7</b>), and [ZnPt<sub>4</sub>(PPh<sub>3</sub>)<sub>8</sub>(μ<sub>3</sub>-S)<sub>4</sub>][ClO<sub>4</sub>]<sub>2</sub> (<b>8</b>), have been prepared from Pt<sub>2</sub>(PPh<sub>3</sub>)<sub>4</sub>(μ-S)<sub>2</sub> (<b>1</b>) with appropriate zinc and cadmium substrates. The structures have been determined by single-crystal X-ray diffraction. The supporting anions play an active role in the structural assembly process. An unexpected disintegration complex [Pt<sub>2</sub>(S<sub>2</sub>CH<sub>2</sub>)Cl(PPh<sub>3</sub>)<sub>4</sub>][PF<sub>6</sub>] (<b>6</b>) has also been isolated and characterized by single-crystal X-ray diffraction. The mechanism of the formation of <b>6</b> is proposed.