Alfred Werner developed the principles of modern coordination chemistry for which he was awarded the 1913 Noble prize in chemistry. A central tenet of coordination chemistry is that the properties of metal complexes can be understood within the context of their primary and secondary coordination spheres. For instance, Werner recognized that both spheres regulate the functional aspects of metal complexes. Since the time of Werner that has been enormous advances in delineating all features of the primary coordination sphere, including how metal-ligand interactions affect the structural and functional properties of complexes. Less is known about the impact of the secondary coordination sphere on reactivity. My group has prepared several types of metal complexes that are designed to regulate both coordination spheres with highly anionic multidentate ligands that create rigid structures proximal to a metal center. Our systems have focused on obtaining discrete metal complexes, investigating their reactivity with small molecules, such as dioxygen, and understanding reaction mechanisms. This presentation will describe our findings that illustrate key concepts of how the secondary coordination sphere influences the coordination chemistry of transition metal complexes.

Regulating the primary and secondary coordination spheres in coordination complexes

246th National Meeting (2013)

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