Most coordination chemistry that has been studied with the actinide series has only utilized ligands stable to oxygen and moisture due to the scarcity and radiation hazards associated with these elements. Additionally, the non-aqueous chemistry of the transuranic elements is relatively unexplored and offers a wider platform for exploring methods of deducing electronic structure and information about the actinide-ligand bond. Such information can be very useful for discovering trends in the whole series. In the reported work, a series (Th-Cf) of complexes using the redox active ligand 2,4,6,8-tetrakis(tert-butyl)-9-hydroxyphenoxanone (HDOPO) were synthesized in non-aqueous conditions under an inert atmosphere and have been fully characterized with the help of X-ray, optical, magnetic, and computational techniques. Crystallographic data reveal An(DOPO)3 complexes, yet U, Np, and Pu are clearly not in the same oxidation state as Am(III) and Cf(III). Furthermore, the Cf(III) complex disrupts the tris-chelate trend due to radiolysis. It is also shown that the ligand undergoes redox transitions to stabilize the higher oxidation states of the earlier actinides. The results will help contribute toward gaining foundational knowledge of structure and bonding in non-aqueous transuranic chemistry as well as give insight into the participation of f-orbitals in bonding.

Investigation of covalency in the transuranic elements under non-aqueous conditions

254th National Meeting (2017)

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