Synthesis, Structure and Catalytic Properties of Hyp₃[Ge₉Rh]PPh₃

Abstract In single‐site homogeneous catalysts (SSHoCs) transition metal atoms are incorporated in the surface of a small homoatomic atom cluster. Within this concept the main group element cluster is considered as innocent support material, while the catalysis itself is realised at the transition metal atom. In the case of [Ge 9 ] clusters both, transition metal atom and the Ge atoms have low oxidation states. Thus, improving the synthesis towards transition metal decorated Zintl cluster has become important in the last years, and the catalytic activity of these clusters is of high interest. An optimised one‐step synthetic protocol for Hyp 3 [Ge 9 Rh]PPh 3 is presented. The product is characterised by NMR spectroscopy, LIFDI/MS and single crystal structure determination. The Rh atom is incorporated in the clusters surface and bridges a deltahedral cluster face, whereby one of the triangular edges opens forming an almost planar face of three Ge and one Rh atom. PPh 3 ligand dissociation, the catalytic activity in the isomerisation of 1‐hexene as well as allylbenzene, andthe hydrogenation of those substrates with hydrogen is investigated.