Reactions of Zintl ion Pb9 with Gold Precursor PPh3AuCl

Abstract

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.