Metalloenzymes are capable of activating strong C—H bonds (up to 104 kcal/mol) with first-row transition metal ions. This ability is a result of the excellent control over both the primary and secondary coordination sphere around the transition metal ion. The primary coordination sphere is controlled by the type of ligands and this governs the electronic and electrochemical properties of the metal ion. The secondary coordination sphere is controlled through non-covalent interactions, such as hydrogen bonds and these can result in substrate selectivity. This talk will describe the synthesis and characterization of a series of CoII—OH complexes with varied primary coordination spheres with hydrogen bonding cavities. These CoII—OH complexes have trigonal symmetry and use a tris(2-aminoethyl)amine backbone. Two new hybrid tetradente tripodal ligands were prepared and characterized with both urea and sulfonamide donors. The molecular structures of three of the four complexes were determined by X-ray diffraction methods and show that each complex has a trigonal bipyramidal geometry with hydrogen bonding interactions between the hydroxo and the tripodal ligand. These four ligands lead to changes in electronic, structural, vibronic, and electrochemical properties of the resulting CoII—OH complexes

Modular approach to tuning the equatorial ligand field strength around a series of CoII—OH complexes with hydrogen bonding cavities in trigonal symmetry

251st National Meeting (2016)

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