Covalency-Driven Dimerization of Plutonium(IV) in a Hydroxamate Complex

Mark A. Silver; Samantha K. Cary; Jared T. Stritzinger; T. Gannon Parker; Laurent Maron; Thomas E. Albrecht-Schmitt

doi:10.1021/acs.inorgchem.6b00340

Covalency-Driven Dimerization of Plutonium(IV) in a Hydroxamate Complex

Mark A. Silver, Samantha K. Cary, Jared T. Stritzinger, T. Gannon Parker, Laurent Maron, Thomas E. Albrecht-Schmitt

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

11 Scopus citations

Abstract

The reaction of formohydroxamic acid [NH(OH)CHO, FHA] with Pu^III should result in stabilization of the trivalent oxidation state. However, slow oxidation to Pu^IV occurs, which leads to formation of the dimeric plutonium(IV) formohydroxamate complex Pu₂(FHA)₈. In addition to being reductants, hydroxamates are also strong π-donor ligands. Here we show that formation of the Pu₂(FHA)₈ dimer occurs via covalency between the 5f orbitals on plutonium and the π∗ orbitals of FHA^- anions, which gives rise to a broad and intense ligand-to-metal charge-transfer feature. Time-dependent density functional theory calculations corroborate this assignment.

Original language	English
Pages (from-to)	5092-5094
Number of pages	3
Journal	Inorganic Chemistry
Volume	55
Issue number	11
DOIs	https://doi.org/10.1021/acs.inorgchem.6b00340
State	Published - Jun 6 2016
Externally published	Yes

Funding

This material is based upon work supported by the U.S. Department of Energy, Office of Science, Office of Basic Energy Sciences, Heavy Elements Chemistry Program, under Award DE-FG02-13ER16414. The 242Pu used in this research was supplied by the U.S. Department of Energy, Office of Science, via the Isotope Program in the Office of Nuclear Physics and was provided to Florida State University via the Isotope Development and Production for Research and Applications Program through the Radiochemical Engineering and Development Center at Oak Ridge National Laboratory. L.M. is a member of the Institut Universitaire de France. CalMip is acknowledged for a generous grant of computing time. The ANR, Humboldt Foundation, and Chinese Academy of Sciences are also acknowledged for financial support

Funders	Funder number
U.S. Department of Energy
Alexander von Humboldt-Stiftung
Office of Science
Basic Energy Sciences	DE-FG02-13ER16414
Oak Ridge National Laboratory
Florida State University
Agence Nationale de la Recherche
Chinese Academy of Sciences
Institut universitaire de France

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title = "Covalency-Driven Dimerization of Plutonium(IV) in a Hydroxamate Complex",

abstract = "The reaction of formohydroxamic acid [NH(OH)CHO, FHA] with PuIII should result in stabilization of the trivalent oxidation state. However, slow oxidation to PuIV occurs, which leads to formation of the dimeric plutonium(IV) formohydroxamate complex Pu2(FHA)8. In addition to being reductants, hydroxamates are also strong π-donor ligands. Here we show that formation of the Pu2(FHA)8 dimer occurs via covalency between the 5f orbitals on plutonium and the π∗ orbitals of FHA- anions, which gives rise to a broad and intense ligand-to-metal charge-transfer feature. Time-dependent density functional theory calculations corroborate this assignment.",

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T1 - Covalency-Driven Dimerization of Plutonium(IV) in a Hydroxamate Complex

AU - Silver, Mark A.

AU - Cary, Samantha K.

AU - Stritzinger, Jared T.

AU - Parker, T. Gannon

AU - Maron, Laurent

AU - Albrecht-Schmitt, Thomas E.

PY - 2016/6/6

Y1 - 2016/6/6

N2 - The reaction of formohydroxamic acid [NH(OH)CHO, FHA] with PuIII should result in stabilization of the trivalent oxidation state. However, slow oxidation to PuIV occurs, which leads to formation of the dimeric plutonium(IV) formohydroxamate complex Pu2(FHA)8. In addition to being reductants, hydroxamates are also strong π-donor ligands. Here we show that formation of the Pu2(FHA)8 dimer occurs via covalency between the 5f orbitals on plutonium and the π∗ orbitals of FHA- anions, which gives rise to a broad and intense ligand-to-metal charge-transfer feature. Time-dependent density functional theory calculations corroborate this assignment.

AB - The reaction of formohydroxamic acid [NH(OH)CHO, FHA] with PuIII should result in stabilization of the trivalent oxidation state. However, slow oxidation to PuIV occurs, which leads to formation of the dimeric plutonium(IV) formohydroxamate complex Pu2(FHA)8. In addition to being reductants, hydroxamates are also strong π-donor ligands. Here we show that formation of the Pu2(FHA)8 dimer occurs via covalency between the 5f orbitals on plutonium and the π∗ orbitals of FHA- anions, which gives rise to a broad and intense ligand-to-metal charge-transfer feature. Time-dependent density functional theory calculations corroborate this assignment.

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DO - 10.1021/acs.inorgchem.6b00340

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JO - Inorganic Chemistry

JF - Inorganic Chemistry

IS - 11

ER -

Covalency-Driven Dimerization of Plutonium(IV) in a Hydroxamate Complex

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