Redox reactions accompanied by proton transfer are ubiquitous and crucial in almost all applications. Metalloenzymes are able to facilitate various proton/electron delivery motifs in the active site. However, in synthetic systems, protonation near the metal center often results in a prominent positive shift of redox potential, limiting the electron transfer to the substrate. This work describes how secondary coordination sphere pK<sub>a</sub> and ligand-based redox potentials are coupled/uncoupled, as well as how they regulate proton and electron transfer activity. A family of Fe(PDI) complexes with pendant bases in the secondary coordination sphere were synthesized and characterized. The pK<sub>a</sub> of these pendant bases were measured and the cyclic voltammetry were performed to investigate the reduction potentials of the ligand-based redox events. Proton and electron transfer reactions to substrate were explored and will be discussed.

Ligand-based reductions in iron pyridinediimine complexes with protonated secondary coordination spheres

255th National Meeting (2018)

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