Interpolymetallic Assembly of d⁸−d¹⁰ Sulfide Aggregates from [Pt₂(PPh₃)₄(μ-S)₂] and Group 12 Metals

A series of heterometallic Pt−M (M = Zn and Cd) sulfide aggregates with growing nuclearities {Pt2M}, {Pt4M}, and {Pt4M2}, viz., [ZnPt2Cl2(PPh3)4(μ3-S)2] (2), [CdPt2Cl2(PPh3)4(μ3-S)2] (3), [Pt2(PPh3)4(μ3-S)2]2[ZnSO4]2 (4), [Pt2(PPh3)4(μ3-S)2]2[CdSO4]2·H2O (5), [CdPt4(PPh3)8(μ3-S)4][ClO4]2 (7), and [ZnPt4(PPh3)8(μ3-S)4][ClO4]2 (8), have been prepared from Pt2(PPh3)4(μ-S)2 (1) 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 [Pt2(S2CH2)Cl(PPh3)4][PF6] (6) has also been isolated and characterized by single-crystal X-ray diffraction. The mechanism of the formation of 6 is proposed.