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

Abstract

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 ligandmore » 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.« less

Authors:
 [1];  [2]; ORCiD logo [2]; ORCiD logo [3];  [3]; ORCiD logo [3];  [4];  [3];  [1];  [5]; ORCiD logo [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)
Publication Date:
Research Org.:
SLAC National Accelerator Laboratory (SLAC), Menlo Park, CA (United States)
Sponsoring Org.:
USDOE Office of Science (SC), Basic Energy Sciences (BES)
OSTI Identifier:
1470936
Grant/Contract Number:  
AC02-76SF00515; SC0008479; SC0017259
Resource Type:
Accepted Manuscript
Journal Name:
Inorganic Chemistry
Additional Journal Information:
Journal Volume: 57; Journal Issue: 11; Journal ID: ISSN 0020-1669
Publisher:
American Chemical Society (ACS)
Country of Publication:
United States
Language:
English
Subject:
37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY

Citation Formats

Pattenaude, Scott A., Mullane, Kimberly C., Schelter, Eric J., Ferrier, Maryline G., Stein, Benjamin W., Bone, Sharon E., Lezama Pacheco, Juan S., Kozimor, Stosh A., Fanwick, Phillip E., Zeller, Matthias, and Bart, Suzanne C. Redox-Active vs Redox-Innocent: A Comparison of Uranium Complexes Containing Diamine Ligands. United States: N. p., 2018. Web. doi:10.1021/acs.inorgchem.8b00663.
Pattenaude, Scott A., Mullane, Kimberly C., Schelter, Eric J., Ferrier, Maryline G., Stein, Benjamin W., Bone, Sharon E., Lezama Pacheco, Juan S., Kozimor, Stosh A., Fanwick, Phillip E., Zeller, Matthias, & Bart, Suzanne C. Redox-Active vs Redox-Innocent: A Comparison of Uranium Complexes Containing Diamine Ligands. United States. https://doi.org/10.1021/acs.inorgchem.8b00663
Pattenaude, Scott A., Mullane, Kimberly C., Schelter, Eric J., Ferrier, Maryline G., Stein, Benjamin W., Bone, Sharon E., Lezama Pacheco, Juan S., Kozimor, Stosh A., Fanwick, Phillip E., Zeller, Matthias, and Bart, Suzanne C. Fri . "Redox-Active vs Redox-Innocent: A Comparison of Uranium Complexes Containing Diamine Ligands". United States. https://doi.org/10.1021/acs.inorgchem.8b00663. https://www.osti.gov/servlets/purl/1470936.
@article{osti_1470936,
title = {Redox-Active vs Redox-Innocent: A Comparison of Uranium Complexes Containing Diamine Ligands},
author = {Pattenaude, Scott A. and Mullane, Kimberly C. and Schelter, Eric J. and Ferrier, Maryline G. and Stein, Benjamin W. and Bone, Sharon E. and Lezama Pacheco, Juan S. and Kozimor, Stosh A. and Fanwick, Phillip E. and Zeller, Matthias and Bart, Suzanne C.},
abstractNote = {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.},
doi = {10.1021/acs.inorgchem.8b00663},
journal = {Inorganic Chemistry},
number = 11,
volume = 57,
place = {United States},
year = {2018},
month = {5}
}

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Figure 1 Figure 1: Uranium complexes featured in this study.

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