A new redox-active Schiff base ligand framework, “phen-BIAN” (N,N’-bis(iminophenol)acenaphthene) has been established. This ligand system combines the redox-active α-diimine backbone of Ar-BIANs with the mixed-donor O-N-N-O salen-type binding pocket. A series of transition metal and uranyl (UO22+) phen-BIAN complexes has been prepared and characterized through single crystal x-ray diffraction and electrochemical studies. Several unique features are observed for the uranyl complexes, including a variety of solvent-dependent solid-state structures with unusual oxo contacts to CH2Cl2 and CHCl3, and rich electrochemical behavior consistent with the formation of mixed valent U(VI)/U(V) and U(V)/U(IV) species in solution. These data suggest the phen-BIAN framework is a suitable tool for accessing and studying the coordination chemistry and redox behavior of lower-valent uranium complexes.

Coordination chemistry and redox-activity of uranium complexes of tetradentate BIAN-type ligands

255th National Meeting (2018)

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