Pt4S4 Clusters with Functionalized Thiosemicarbazones derived from 5‐Acetylbarbituric Acid

Abstract

AbstractReaction of K2[PtCl4] with thiosemicarbazones derived from 5‐acetylbarbituric acid led to the isolation of the tetranuclear species [Pt(AcbM)]4 · 2/2DMSO · 2DMSO · 5H2O (1) and [Pt(AcbE)]4 · 4DMSO · 2H2O (2) (H2AcbM = 5‐acetylbarbituric‐4N‐methyl thiosemicarbazone and H2AcbE = 5‐acetylbarbituric‐4N‐ethyl thiosemicarbazone). Both of these compounds feature a Pt4S4 cluster in which some of the Pt–Pt distances suggest the existence of weak metal‐metal interactions. Crystals of these tetranuclear species are stabilized by intermolecular π‐π stacking interactions. The two compounds have almost equivalent molecular structures, differing only in the orientation of the substituent on the amine nitrogen atom of the thiosemicarbazone. The two tetranuclear complexes contain the thiosemicarbazone bonded as a terdentate ligand to the platinum atom through the thiolate sulfur atom, the azomethine nitrogen atom and the alcoholate oxygen atom of the 5‐acetylbarbiturate function.