Synthesis of Tyrosine-involved Corrole Cu(III), Mn(IV), and Mn(III) Complexes As Biomimetic Models of Oxygen Evolving Complex in Photosystem II

Boc-protected tyrosine-attached corrole ligand on the "ortho" position compound 3, its corresponding copper (III) 4a, manganese (IV) 4b, and manganese (III) 4c complexes have been designed and synthesized based on the structures of active-centers of related biological systems. H-1 NMR and electronic absorption spectra of these metal complexes are investigated. The crystal structure of 4a displays the relative position of TyrOH unit to the high valent metal center. Electrochemistry investigations display the possibilities of intramolecular electron or energy transfer between TyrOH group and metal corrole group.