Redox-Active Vs Redox-Innocent: A Comparison Of Uranium Complexes Containing Diamine Ligands

Uranium complexes ((MeS)DAE)(2)U(THF) (1-DAE) and Cp2U((MeS)DAE) (2-DAE) ((Mes)DAE = [ArN-CH2CH2-NAr]; Ar = 2,4,6-trimethylphenyl (Mes)), bearing redox-innocent diamide ligands, have been synthesized and characterized for a full comparison with previously published, redox-active diimine complexes, ((Mes)DABMe)2" U(THF) (1 DAB) and Cp2U(m"DAB'') (2-DAB) (MeSDABMe = [ArN=C(Me)C(Me)=NAr]; Ar = Mes). These redoxinnocent analogues maintain an analogous steric environment to their redox-active ligand counterparts to facilitate a study aimed at determining the differing electronic behavior around the uranium center. Structural analysis by X-ray crystallography showed 1-DAE and 2-DAE have a structural environment very similar to 1-DAB and 2-DAB, respectively. The main difference occurs with coordination of the ene-backbone to the uranium center in the latter species. Electronic absorption spectroscopy reveals these new DAE complexes are nearly identical to each other. X-ray absorption spectroscopy suggests all four species contain +4 uranium ions. The data also indicates that there is an electronic difference between the bis(diamide)-THF uranium complexes as opposed to those that only contain one diamide and two cyclopentadienyl rings. Finally, magnetic measurements reveal that all complexes display temperature-dependent behavior consistent with uranium(1V) ions that do not include ligand radicals. Overall, this study determines that there is no significant bonding difference between the redox-innocent and redox-active ligand frameworks on uranium. Furthermore, there are no data to suggest covalent bonding character using the latter ligand framework on uranium, despite what is known for transition metals.