A New Synthetic Methodology in the Preparation of Bimetallic Chalcogenide Clusters via Cluster-to-Cluster Transformations |
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| Authors: | Yu-Jie Zhong Jian-Hong Liao Tzu-Hao Chiu Yuh-Sheng Wen C W Liu |
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| Institution: | 1.Department of Chemistry, National Dong Hwa University, Hualien 974301, Taiwan; (Y.-J.Z.); (J.-H.L.); (T.-H.C.);2.Institute of Chemistry, Academia Sinica, Taipei 11528, Taiwan; |
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| Abstract: | A decanuclear silver chalcogenide cluster, Ag10(Se){Se2P(OiPr)2}8] (2) was isolated from a hydride-encapsulated silver diisopropyl diselenophosphates, Ag7(H){Se2P(OiPr)2}6], under thermal condition. The time-dependent NMR spectroscopy showed that 2 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, CuxAg10-x(Se){Se2P(OiPr)2}8] (x = 0–7, 3), via heating CuxAg7−x(H){Se2P(OiPr)2}6] (x = 1–6) at 60 °C. Compositions of 3 were accurately confirmed by the ESI mass spectrometry. While the crystal 2 revealed two un-identical Ag10(Se){Se2P(OiPr)2}8] structures in the asymmetric unit, a co-crystal of Cu3Ag7(Se){Se2P(OiPr)2}8]0.6Cu4Ag6(Se){Se2P(OiPr)2}8]0.4 (3a]0.63b]0.4) was eventually characterized by single-crystal X-ray diffraction. Even though compositions of 2, 3a]0.63b]0.4 and the previous published Ag10(Se){Se2P(OEt)2}8] (1) are quite similar (10 metals, 1 Se2−, 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. |
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| Keywords: | chalcogenide hydride silver copper inverse coordination |
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