Jiayao Zhang

• This thesis is divided into six chapters. Chapter I generally introduces the historical background, structural aspects, properties, and applications of POMs, the state of the art of polyoxo-noble-metalates, noble-metal-containing POMs and arsenic compound, as well as the motivation to perform this work. Chapter II includes the information of applied analytical techniques and synthetic procedures for the used POM and organorhodium(III) precursors. Chapter III is devoted to polyoxoplatinate, polyoxopalladate and mixed polyoxo-noble-metalates, and 7 novel polyoxo-noble-metalates have been obtained with the following highlights: (i) The first PtIV-containing discrete polyoxoplatinate(II) Pt7 and polyoxopalladate(II) PtPd6 have been prepared and characterized in the solid-state, in solution, and in the gas phase; (ii) The first discrete mixed platinum(IV)-gold(III) oxoanion Pt2Au3 was structurally characterized in the solid state by single-crystal XRD and TGA, and in solution by multinuclear NMR and ESI-MS studies. Chapter IV presents 3 novel Platinum(II/III)-containing isopolytungstates. The polyoxoanion Pt3W11 consists of three {W3O13} and one {W2O10} fragments connected by three Pt(II) atoms forming linear {Pt3O12} triad. The polyoxoanion PtII2W5 and PtIII2W5 both consists of one lacunary Lindqvist fragments {W5O18}6− coordinated by two Pt(II) in square planar coordination and two Pt(III) with direct Pt–Pt bonding, respectively. Chapter V describes the synthesis of three all-inorganic platinum arenate(III) compound. The first two full inorganic discrete platinum arsenate(III) clusters: PtAs6 and Pt4As8, have been synthesized in aqua media. In Pt4As8, Each Pt atom is coordinated by two O atoms and two As atoms involved in direct As-Pt bonding. And a platinum arsenate(III) heteropolytungstate Pt2As6W4 has been synthesized in aqua media and characterized by 195Pt NMR.Chapter VI deals with the synthesis and characterization of two RhCp*-containing heteropolytungstates.