Inter- and hetero-metallic assembly of palladium sulfide aggregates: crystal and molecular structures of [InPd2Cl3(dppf)2(μ3-S)2] · 3CH2Cl2 and [Ag2Pd2(NO3)2(dppf)2(μ3-S)2] · 2CH2Cl2

Lewis acid/base addition between Pd2(dppf)2(μ-S)2 and MXn [M = In(III), Ga(III), Tl(I), Pb(II), Sn(IV), Bi(III), Ag(I) and Au(I); X = halide or pseudohalide; dppf = 1,1′-bis(diphenylphosphino)ferrocene] gives rise to a range of neutral or cationic intermetallics aggregates with the {Pd2MS2} or {Pd2M2S2} core. Effectively Pd2(dppf)2(μ-S)2 functions as a chelating or bridging dithio metalloligand. Two representative crystal structures, viz. [InPd2Cl3(dppf)2(μ3-S)2] · 3CH2Cl2 and [Ag2Pd2(NO3)2(dppf)2(μ3-S)2] · 2CH2Cl2 are described and discussed. The former features an intermetallic {InPd2} triangle whereas the latter displays a heterometallic {Ag2Pd2} metal plane. Both of them are sustained and supported by capping sulfides without significant or direct metal–metal bonds.