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