ORGANO-F-ELEMENT THERMOCHEMISTRY - IMPLICATIONS FOR REACTIVITY AND BONDING FROM METAL-LIGAND BONDING ENERGETICS

This article surveys the termochemistry of organolanthanide and organoactinide complexes in several interrelated areas. For trivalent 4f and tetravalent 5f as well as tetravalent (d°) group 4 complexes, patterns in metal-ligand s bond enthalpies are rather similar for a diverse range of ligands. This information is directly applicable to the analysis and invention of a variety of stoichiometric and catalytic transformations, including olefin hydroamination, hydrophosphination, and hydrosilylation, as well as dehydrogenative silane polymerization. Studies of metal-ligand bonding energetics in zero-valent lanthanide and group 4 bisarene sandwich complexes reveal metal-arene bonding which is both similar and rather strong.