Using Redox-Active Ligands to Generate Actinide Ligand Radical Species

Shane S. Galley; Scott A. Pattenaude; Debmalya Ray; Carlo Alberto Gaggioli; Megan A. Whitefoot; Yusen Qiao; Robert F. Higgins; W. L. Nelson; Ryan Baumbach; Joseph M. Sperling; Matthias Zeller; Tyler S. Collins; Eric J. Schelter; Laura Gagliardi; Thomas E. Albrecht-Schönzart; Suzanne C. Bart

doi:10.1021/acs.inorgchem.1c01766

Using Redox-Active Ligands to Generate Actinide Ligand Radical Species

Shane S. Galley, Scott A. Pattenaude, Debmalya Ray, Carlo Alberto Gaggioli, Megan A. Whitefoot, Yusen Qiao, Robert F. Higgins, W. L. Nelson, Ryan Baumbach, Joseph M. Sperling, Matthias Zeller, Tyler S. Collins, Eric J. Schelter, Laura Gagliardi, Thomas E. Albrecht-Schönzart, Suzanne C. Bart

Research output: Contribution to journal › Article › peer-review

22 Scopus citations

Abstract

Using a redox-active dioxophenoxazine ligand, DOPO (DOPO = 2,4,6,8-tetra-tert-butyl-1-oxo-1H-phenoxazine-9-olate), a family of actinide (U, Th, Np, and Pu) and Hf tris(ligand) coordination compounds was synthesized. The full characterization of these species using 1H NMR spectroscopy, electronic absorption spectroscopy, SQUID magnetometry, and X-ray crystallography showed that these compounds are analogous and exist in the form M(DOPOq)2(DOPOsq), where two ligands are of the oxidized quinone form (DOPOq) and the third is of the reduced semiquinone (DOPOsq) form. The electronic structures of these complexes were further investigated using CASSCF calculations, which revealed electronic structures consistent with metals in the +4 formal oxidation state and one unpaired electron localized on one ligand in each complex. Furthermore, f orbitals of the early actinides show a sizable bonding overlap with the ligand 2p orbitals. Notably, this is the first example of a plutonium-ligand radical species and a rare example of magnetic data being recorded for a homogeneous plutonium coordination complex.

Original language	English
Pages (from-to)	15242-15252
Number of pages	11
Journal	Inorganic Chemistry
Volume	60
Issue number	20
DOIs	https://doi.org/10.1021/acs.inorgchem.1c01766
State	Published - Oct 18 2021
Externally published	Yes

Funding

This work was funded by the Division of Chemical Sciences, Geosciences, and Biosciences, Office of Basic Energy Sciences of the U.S. Department of Energy through Grants DESC0008479 (S.C.B.), DE-SC002183 (L.G.), DEFG02-13ER16414 (T.E.A.S.), and DE-SC0017259 (E.J.S.). D.R., C.A.G, and L.G. used resources of the Minnesota Supercomputing Institute to perform all the calculations. Acquisition of the plutonium magnetic data was supported by the Center for Actinide Science and Technology (CAST), which is an Energy Frontier Research Centre (EFRC) funded by the U.S. Department of Energy (DOE), Office of Science, Basic Energy Sciences (BES) under Award DE-SC0016568. Work done by R.B. was performed at the National High MAgnetic Field LAboratory, which is supported by the National Science Foundation Cooperative Agreement No. DMR-1644779 and the State of Florida. The X-ray diffractometer at Purdue University used for structure determination of 1-Hf , 1-U , and 1-Th was funded by the National Science Foundation through the Major Research Instrumentation Program under Grant CHE 1625543. We also thank Prof. Jay Kikkawa (UPenn Physics) for assistance with the magnetic measurements.

Funders	Funder number
Center for Actinide Science and Technology
Energy Frontier Research Centre
State of Florida	CHE 1625543
National Science Foundation	DMR-1644779
U.S. Department of Energy	DESC0008479, DEFG02-13ER16414, DE-SC002183, DE-SC0017259
Office of Science
Basic Energy Sciences	DE-SC0016568
Chemical Sciences, Geosciences, and Biosciences Division

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Galley, S. S., Pattenaude, S. A., Ray, D., Gaggioli, C. A., Whitefoot, M. A., Qiao, Y., Higgins, R. F., Nelson, W. L., Baumbach, R., Sperling, J. M., Zeller, M., Collins, T. S., Schelter, E. J., Gagliardi, L., Albrecht-Schönzart, T. E., & Bart, S. C. (2021). Using Redox-Active Ligands to Generate Actinide Ligand Radical Species. Inorganic Chemistry, 60(20), 15242-15252. https://doi.org/10.1021/acs.inorgchem.1c01766

@article{95198be999cd4eceb60c8714704532ab,

title = "Using Redox-Active Ligands to Generate Actinide Ligand Radical Species",

abstract = "Using a redox-active dioxophenoxazine ligand, DOPO (DOPO = 2,4,6,8-tetra-tert-butyl-1-oxo-1H-phenoxazine-9-olate), a family of actinide (U, Th, Np, and Pu) and Hf tris(ligand) coordination compounds was synthesized. The full characterization of these species using 1H NMR spectroscopy, electronic absorption spectroscopy, SQUID magnetometry, and X-ray crystallography showed that these compounds are analogous and exist in the form M(DOPOq)2(DOPOsq), where two ligands are of the oxidized quinone form (DOPOq) and the third is of the reduced semiquinone (DOPOsq) form. The electronic structures of these complexes were further investigated using CASSCF calculations, which revealed electronic structures consistent with metals in the +4 formal oxidation state and one unpaired electron localized on one ligand in each complex. Furthermore, f orbitals of the early actinides show a sizable bonding overlap with the ligand 2p orbitals. Notably, this is the first example of a plutonium-ligand radical species and a rare example of magnetic data being recorded for a homogeneous plutonium coordination complex.",

author = "Galley, {Shane S.} and Pattenaude, {Scott A.} and Debmalya Ray and Gaggioli, {Carlo Alberto} and Whitefoot, {Megan A.} and Yusen Qiao and Higgins, {Robert F.} and Nelson, {W. L.} and Ryan Baumbach and Sperling, {Joseph M.} and Matthias Zeller and Collins, {Tyler S.} and Schelter, {Eric J.} and Laura Gagliardi and Albrecht-Sch{\"o}nzart, {Thomas E.} and Bart, {Suzanne C.}",

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year = "2021",

month = oct,

day = "18",

doi = "10.1021/acs.inorgchem.1c01766",

language = "English",

volume = "60",

pages = "15242--15252",

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Galley, SS, Pattenaude, SA, Ray, D, Gaggioli, CA, Whitefoot, MA, Qiao, Y, Higgins, RF, Nelson, WL, Baumbach, R, Sperling, JM, Zeller, M, Collins, TS, Schelter, EJ, Gagliardi, L, Albrecht-Schönzart, TE & Bart, SC 2021, 'Using Redox-Active Ligands to Generate Actinide Ligand Radical Species', Inorganic Chemistry, vol. 60, no. 20, pp. 15242-15252. https://doi.org/10.1021/acs.inorgchem.1c01766

TY - JOUR

T1 - Using Redox-Active Ligands to Generate Actinide Ligand Radical Species

AU - Galley, Shane S.

AU - Pattenaude, Scott A.

AU - Ray, Debmalya

AU - Gaggioli, Carlo Alberto

AU - Whitefoot, Megan A.

AU - Qiao, Yusen

AU - Higgins, Robert F.

AU - Nelson, W. L.

AU - Baumbach, Ryan

AU - Sperling, Joseph M.

AU - Zeller, Matthias

AU - Collins, Tyler S.

AU - Schelter, Eric J.

AU - Gagliardi, Laura

AU - Albrecht-Schönzart, Thomas E.

AU - Bart, Suzanne C.

PY - 2021/10/18

Y1 - 2021/10/18

N2 - Using a redox-active dioxophenoxazine ligand, DOPO (DOPO = 2,4,6,8-tetra-tert-butyl-1-oxo-1H-phenoxazine-9-olate), a family of actinide (U, Th, Np, and Pu) and Hf tris(ligand) coordination compounds was synthesized. The full characterization of these species using 1H NMR spectroscopy, electronic absorption spectroscopy, SQUID magnetometry, and X-ray crystallography showed that these compounds are analogous and exist in the form M(DOPOq)2(DOPOsq), where two ligands are of the oxidized quinone form (DOPOq) and the third is of the reduced semiquinone (DOPOsq) form. The electronic structures of these complexes were further investigated using CASSCF calculations, which revealed electronic structures consistent with metals in the +4 formal oxidation state and one unpaired electron localized on one ligand in each complex. Furthermore, f orbitals of the early actinides show a sizable bonding overlap with the ligand 2p orbitals. Notably, this is the first example of a plutonium-ligand radical species and a rare example of magnetic data being recorded for a homogeneous plutonium coordination complex.

AB - Using a redox-active dioxophenoxazine ligand, DOPO (DOPO = 2,4,6,8-tetra-tert-butyl-1-oxo-1H-phenoxazine-9-olate), a family of actinide (U, Th, Np, and Pu) and Hf tris(ligand) coordination compounds was synthesized. The full characterization of these species using 1H NMR spectroscopy, electronic absorption spectroscopy, SQUID magnetometry, and X-ray crystallography showed that these compounds are analogous and exist in the form M(DOPOq)2(DOPOsq), where two ligands are of the oxidized quinone form (DOPOq) and the third is of the reduced semiquinone (DOPOsq) form. The electronic structures of these complexes were further investigated using CASSCF calculations, which revealed electronic structures consistent with metals in the +4 formal oxidation state and one unpaired electron localized on one ligand in each complex. Furthermore, f orbitals of the early actinides show a sizable bonding overlap with the ligand 2p orbitals. Notably, this is the first example of a plutonium-ligand radical species and a rare example of magnetic data being recorded for a homogeneous plutonium coordination complex.

UR - http://www.scopus.com/inward/record.url?scp=85117116384&partnerID=8YFLogxK

U2 - 10.1021/acs.inorgchem.1c01766

DO - 10.1021/acs.inorgchem.1c01766

M3 - Article

C2 - 34569783

AN - SCOPUS:85117116384

SN - 0020-1669

VL - 60

SP - 15242

EP - 15252

JO - Inorganic Chemistry

JF - Inorganic Chemistry

IS - 20

ER -

Using Redox-Active Ligands to Generate Actinide Ligand Radical Species

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