A New Synthetic Methodology in the Preparation of Bimetallic Chalcogenide Clusters via Cluster-to-Cluster Transformations.

A decanuclear silver chalcogenide cluster, [Ag(Se){SeP(OPr)}] () was isolated from a hydride-encapsulated silver diisopropyl diselenophosphates, [Ag(H){SeP(OPr)}], under thermal condition. The time-dependent NMR spectroscopy showed that was generated at the first three hours and the hydrido silver cluster was completely consumed after thirty-six hours. This method illustrated as cluster-to-cluster transformations can be applied to prepare selenide-centered decanuclear bimetallic clusters, [CuAg(Se){SeP(OPr)}] (x = 0-7, ), via heating [CuAg(H){SeP(OPr)}] (x = 1-6) at 60 °C. Compositions of were accurately confirmed by the ESI mass spectrometry. While the crystal revealed two un-identical [Ag(Se){SeP(OPr)}] structures in the asymmetric unit, a co-crystal of [CuAg(Se){SeP(OPr)}][CuAg(Se){SeP(OPr)}] ([][]) was eventually characterized by single-crystal X-ray diffraction. Even though compositions of , [][] and the previous published [Ag(Se){SeP(OEt)}] () are quite similar (10 metals, 1 Se, 8 ligands), their metal core arrangements are completely different. These results show that different synthetic methods by using different starting reagents can affect the structure of the resulting products, leading to polymorphism.