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

Abstract

A series of heterometallic Pt-M (M = Zn and Cd) sulfide aggregates with growing nuclearities {Pt2M}, {Pt4M}, and {Pt 4M2}, viz., [ZnPt2Cl2(PPh 3)4(μ3-S)2] (2), [CdPt 2Cl2(PPh3)4(μ3-S) 2] (3), [Pt2(PPh3)4(μ 3-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(PPh 3)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 [P t2(S 2CH2)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.