Reactions of Zintl ion Pb9 with Gold Precursor PPh3AuCl

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2006-12-10

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Transition metal main group clusters have been studied extensively as models for heterogeneous catalysts and metal surface reactions. In this thesis, reactions of Group 14 Zintl ion cluster Pb94- with the Au precursor Au(PPh3)Cl are studied. A new Pb-Au cluster [Pb@Au8] and Zintl ion Pb52- have been isolated. [Pb@Au8] is the first isolated highly symmetric Pb-Au cluster, which has remarkable unit cell dimensions and a nearly perfect cubic structure. XPS spectroscopy was used to demonstrate the existence of the Pb atom in the complex. Zintl ion [Pb5]2- was also synthesized in this study. We successfully characterized it by XRD and 207Pb NMR for the first time. An exciting stable 207Pb NMR signal for Pb52- was found. The other NMR signal is expected based on the population statistical calculation for the two kinds of Pb atoms in Pb52-. The 207Pb NMR analysis also gives important knowledge about the dynamic behavior of the cluster anions.

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