Organometallic f-block compounds have shown many interesting small molecule activation reactions, including hydrocarbon C-H bond cleavage, and the study of interactions of f-block cations with soft hydrocarbon and arene ligands provides important contributions to the understanding of covalency in f-element ligand bonding that is needed for nuclear waste handling. We will present new f-block complexes with simple ligands that bind and reduce arenes spontaneously, even at room temperature, forming inverse arene sandwich complexes. The arenes are sufficiently activated, and the conditions sufficiently mild, that a regioselective C-H bond functionalisation with boranes is possible. This has allowed studies of the catalytic capabilities of these complexes, and the first f-element catalysed catalytic alkyne cyclotrimerisation reactions. Details of the mechanism, requirements for the ancillary ligands, and C-H bonding interactions with the metal centre will be shown. One of the factors that drives the chemistry is the favourability of δ-symmetry bonding interactions with the π-system. We will show new chemistry of a macrocyclic ligand (meso-octamethyl-trans-calix[2]benzene[2]pyrrolide) that exploits this feature in the formation of new bis(arene)sandwich-like geometries, as well as forming complexes with close metal-metal distances.

Actinide-arene interactions and their use in carbon-element bond forming reactions

249th National Meeting (2015)

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