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.