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Redox-Active vs Redox-Innocent: A Comparison of Uranium Complexes Containing Diamine Ligands

Journal Article · · Inorganic Chemistry
 [1];  [2];  [2];  [3];  [3];  [3];  [4];  [3];  [1];  [5];  [1]
  1. Purdue Univ., West Lafayette, IN (United States)
  2. Univ. of Pennsylvania, Philadelphia, PA (United States)
  3. Los Alamos National Lab. (LANL), Los Alamos, NM (United States)
  4. Stanford Univ., Stanford, CA (United States)
  5. Purdue Univ., West Lafayette, IN (United States); Youngstown State Univ., Youngstown, OH (United States)
+ Show Author Affiliations
Here 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.
Research Organization:
SLAC National Accelerator Laboratory (SLAC), Menlo Park, CA (United States)
Sponsoring Organization:
USDOE Office of Science (SC), Basic Energy Sciences (BES) (SC-22)
Grant/Contract Number:
AC02-76SF00515; SC0008479; SC0017259
OSTI ID:
1470936
Journal Information:
Inorganic Chemistry, Journal Name: Inorganic Chemistry Journal Issue: 11 Vol. 57; ISSN 0020-1669
Publisher:
American Chemical Society (ACS)Copyright Statement
Country of Publication:
United States
Language:
English

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Cited By (3)

Ruthenium (II) complexes bearing thioether‐appended α‐iminopyridine ligands: Arene precursors permit access to κ 2 ‐N,N and κ 3 ‐N,N,S complexes journal January 2020
The coordination chemistry of Cm III , Am III , and Ac III in nitrate solutions: an actinide L 3 -edge EXAFS study journal January 2018
An improved laboratory-based x-ray absorption fine structure and x-ray emission spectrometer for analytical applications in materials chemistry research journal February 2019

Figures / Tables (8)

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Table 1(p. 5)table Table 1
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Table 2(p. 6)table Table 2
Figure 6(p. 7)figure Figure 6

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37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY