Organometallics
Organometallics
5 years ago

Structural Characterization and Redox Activity of a Uranyl Dimer and Transition-Metal Complexes of a Tetradentate BIAN Ligand

Structural Characterization and Redox Activity of a Uranyl Dimer and Transition-Metal Complexes of a Tetradentate BIAN Ligand
Anne E. V. Gorden, John D. Gorden, Byron H. Farnum, Julie E. Niklas
The synthesis and characterization of a new ligand system combining the redox-active backbone of Ar-BIANs (N,N′-bis[(aryl)imino]acenaphthenes) and a mixed-donor O–N–N–O salen-type binding pocket is reported. Complexes of Co2+, Ni2+, and UO22+ were prepared and characterized through single-crystal X-ray diffraction and electrochemical studies. The Ni2+ and Co2+ complexes have been used as references against which to compare the unique behaviors exhibited by the uranyl (UO22+) complex, as the latter forms two distinct solid-state structures with unusual oxo contacts to CH2Cl2 and CHCl3 and displays a rich electrochemical profile that indicates a wide range of accessible metal oxidation states through the formation of mixed-valent U(VI)/U(V) and U(V)/U(IV) species in solution.

Publisher URL: http://dx.doi.org/10.1021/acs.organomet.7b00454

DOI: 10.1021/acs.organomet.7b00454

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