Genuine examples of tetrahedral tetradentate sulfide ligand bridging four Pd atoms: controlled formation of [(mu(4)-S){(mu(2)-X)Pd(2)(C(wedge)N)(2)}(2)] (X = OH or Cl; HC(wedge)N = p-C(2)H(5)OC(6)H(4)CH=NC(6)H(4)-p-C(2)H(5)) complexes.

A smooth reaction of [(mu3-S)(mu3-OH)Pd3(CwedgeN)3] (2) with [(mu2-X)2Pd2(CwedgeN)2] (2:1; HCwedgeN = p-C2H5OC6H4CH=NC6H4-p-C2H5, X = OH, Cl) provides [(mu4-S){(mu2-OH)Pd2(CwedgeN)2}2] (3) and [(mu4-S)(mu2-Cl)(mu2-OH)Pd4(CwedgeN)4] (4). Treatment of 3 with HCl (molar ratio 1:2) leads to the corresponding tetranuclear complex [(mu4-S)(mu2-Cl)2Pd4(CwedgeN)4] (5). The three complexes contain a (mu4-S)Pd4 core. A density functional theory study of the bonds in 3 supports that the bonding of the S atom can be described in terms of four two-center two-electron S-Pd bonds, in contrast to most other (mu4-S)M4 systems in the literature, where the presence of M-M bonds prevents a bond-localized description of the molecule. The X-ray structures of 2, 3, and 5 are reported.