Pentadienyl ligands for the stabilization of unusual oxidation states and as directing ligands in homogenous catalysis

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Pentadienyl (Pdl)- ligands are excellent δ-acceptors and therefore well-suited for the stabilization of metal complexes in low oxidation states. This property will be used to prepare chiral and achiral pentadienyl complexes of the early and late transition metals and the rare-earth metals. Besides investigations of the molecular species we also intend to explore the potential of these molecular compounds in “surface organometallic chemistry” (SOMC). In the next step the grafted materials and molecular model complexes will be probed for their synthetic and catalytic potential e.g. towards insertion reactions and the activation and functionalization of small molecules (such as CO, CO2, P4, N2O, N2, CH-bonds). We have already established that Pdl-ligands may also act as di- and trianionic ligand systems, which are formed when attempts were made to access group 4 metal and lanthanide complexes in unusual oxidation states. With respect to these observations we seek a more detailed understanding on the underlying reaction mechanism, but also to probe the reactivity of these species towards small molecules. Major emphasis of our research program is the exploration of the structure-reactivity relationship and the results derived from these studies will guide the potential application of these systems in catalysis and material synthesis.