Non-classical organometallic chemistry and catalysis at actinide centers

In an appropriatedly tuned coordination environment, f-element ions can exhibit high coordinative unsaturation, kinetic lability and electrophilicity. In addition, oxidation state shuttling tendencies, π-bonding abilities, and metal-ligand bond enthalpy orderings differ markedly from those of most middle and late transition metals. One consequence of these non-classical features is a marked propensity for the activation of 2-center 2-electron fragments such as HH and CH fanctionalities. This lecture will focus primarily upon two closely related aspects of saturated hydrocarbon activation at actinide centers: (i) intramo]ecular cyclometalation chemistry involving CH scission on saturated hydrocarbon ligands; (il) activation of exogenous saturated and aromatic hydrocarbon molecules and organometallic molecules by an enthalpy-rich, entropy-poor actinacycle. Important ancillary information is provided by studies of HH and olefin activation. Of central importance in all areas are those structural, electronic and bond enthalpy relationships that control reactivity and selectivity.