Formation and structural relationship of electroactive PtII–HgII polymetallic sulfide aggregates
Abstract
A series of {Pt2HgS2}, {Pt2Hg2S2} and {Pt4HgS4} complexes, viz. [(Ph3P)4Pt2(μ3-S)2HgCl2] 2, [(Ph3P)4Pt2(μ3-S)2Hg(PPh3)]X2 [X = Cl (3a) or PF6 (3b)], [HgPt4(PPh3)8(μ3-S)4]X2 [X = PF6, (4a) or ClO4 (4b)], [Pt2(Ph3P)4(μ3-S)2Hg2(μ-Cl)2Cl2] 5, [(Ph3P)4Pt2(μ3-S)2Hg2(μ-Cl)2(PPh3)2][PF6]26 and [(Ph3P)4Pt2(μ3-S)2Hg2(NO3)2]X2 [X = NO3 (7a) or PF6 (7b)] have been synthesized from [Pt2(μ-S)2(PPh3)4] 1 with the appropriate mercury(II) compounds through 1∶1, 1∶2 and 2∶1 Lewis acid–base additions. Formation of the major product is governed largely by the stoichiometric quantity of the substrates.