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• W2803069989 abstract "Uranium complexes (MesDAE)2U(THF) (1-DAE) and Cp2U(MesDAE) (2-DAE) (MesDAE = [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, (MesDABMe)2U(THF) (1-DAB) and Cp2U(MesDABMe) (2-DAB) (MesDABMe = [ArN═C(Me)C(Me)═NAr]; Ar = Mes). These redox-innocent 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(IV) 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." @default.
• W2803069989 created "2018-05-17" @default.
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• W2803069989 date "2018-05-11" @default.
• W2803069989 modified "2023-10-12" @default.
• W2803069989 title "Redox-Active vs Redox-Innocent: A Comparison of Uranium Complexes Containing Diamine Ligands" @default.
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• W2803069989 doi "https://doi.org/10.1021/acs.inorgchem.8b00663" @default.
• W2803069989 hasPubMedId "https://pubmed.ncbi.nlm.nih.gov/29749729" @default.
• W2803069989 hasPublicationYear "2018" @default.
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