The structure and function of many metalloenzymes are dictated by the secondary coordination sphere, but the precise role(s) of the second sphere to facilitate substrate capture, activation, and stabilization of reactive intermediates remain unknown. Non-covalent interactions of the nitrogenase enzyme are required for biological N2 fixation; however, the lack of synthetic models containing tunable secondary sphere environments for systematic structure/function studies creates an inherent gap in our understanding of the second sphere in biological systems. Our lab addresses this problem by developing discrete metal-ligand platforms with modular secondary spheres to delineate the role(s) of the second sphere on biologically relevant chemical transformations. To this end, we have developed a ligand scaffold amenable to the installation of bifurcated Lewis acidic groups in the second sphere. We will detail the coordination to divalent metal precursors, followed by substrate capture and reactivity. We will address the role(s) of the secondary-sphere groups toward small molecule activation, with a focus on redox transformations of nitrogenous substrates (NxHy). Isolation of secondary sphere stabilized intermediates for nitrogenase-relevant transformations will be described.

Metal-ligand complexes with secondary sphere bifurcated Lewis acids: toward substrate capture and activation

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