Alfred Werner proposed nearly 100 years ago that the secondary coordination sphere has a role in determining physical properties of transition metal complexes.  We now know that the secondary coordination sphere impacts nearly all aspects of transition metal chemistry, including the reactivity and selectivity in metal-mediated processes.  These features are particularly important in the activation of small molecules, such as dioxygen.  There are clear connections between the control of the secondary coordination sphere and the ability of metal complexes to 1) reversibly bind dioxygen or 2) bind and activate dioxygen to form highly reactive M�oxo complexes.  This talk will describe the design of ligand systems that support intramolecular non-covalent interactions within the secondary coordination of metal complexes and show how these effects are used to trap new species, including high valent iron and manganese species with terminal oxo ligands.

Utilizing the secondary coordination sphere to control metal-mediated transformations

242nd National Meeting (2011)

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