The function of metal complexes is linked directly to the local environment (that is, their secondary coordination sphere) in which they are housed. It is now apparent that the placement of compounds within different local environments produces changes in key properties that affect reactivity. It is thus possible to understand function, and dysfunction, of a metal complex within the context of properties associated with their secondary coordination sphere, regardless of system type or length-scale. This presentation will describe architectural features within the secondary coordination sphere that are instrumental in regulating function at a metal center. Protein systems are discussed to illustrate the complexity of molecular structures necessary to promote function, specifically the importance of non-covalent interactions. New methods will be described that combines biotin-streptavidin technology with synthetic inorganic chemistry to develop artificial metalloproteins with active sites that mimic those found in natural proteins. Emphasis will be on the effects of the secondary coordination sphere in which regulation is achieved using intramolecular hydrogen bonds. Structural, spectroscopic, and functional data are presented to characterize the active sites including high resolution molecular structures from X-ray diffraction studies. Our findings demonstrate a viable approach to model protein active sites and stabilize reactive intermediates including metal-peroxido species that are proposed as intermediates in biological oxidations.

Artifical metalloproteins: Developing methods to control the local environments around metal ions

254th National Meeting (2017)

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