Comparison of {O,S}- vs {N,S}-donor ligands in PtNi heterobimetallic lantern complexes

A pair of thiocarboxylate lantern complexes, [PtNi(SAc)4(L)] (L = pyCN (2), HpipCN (3)) and three new {N,S} chelated mercaptopyridine complexes [PtNi(mpyS)4(L)] H2O (4), MeCN (5), (6)) have been synthesized characterized by SCXRD, 1H NMR UV–vis spectroscopies, as well elemental analysis RT solution magnetization. detailed structural comparison was made the {O,S} donor systems that demonstrates stronger field ligand decreases Pt (donor) – M (acceptor) character within lantern, reducing Pt(II) Lewis acidity therefore preventing formation intermolecular interactions in Ni(II) 4–6. An unexpected pentameric species [Pt(PtNi(mpyS)4(Cl))2] (7) also formed, albeit very low quantities, showed importance choice starting material. Additionally, development an improved air- water-stable synthesis for homoleptic, [Pt2(pyS)4], is reported.