title: Covalency-Driven Dimerization of Plutonium(IV) in a Hydroxamate Complex.
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.
authors.affiliation: Department of Chemistry and Biochemistry, Florida State University , Tallahassee, Florida 32306, United States.
authors.forename: Mark A
authors.initials: MA
authors.lastname: Silver
authors.affiliation: Department of Chemistry and Biochemistry, Florida State University , Tallahassee, Florida 32306, United States.
authors.forename: Samantha K
authors.initials: SK
authors.lastname: Cary
authors.affiliation: Department of Chemistry and Biochemistry, Florida State University , Tallahassee, Florida 32306, United States.
authors.forename: Jared T
authors.initials: JT
authors.lastname: Stritzinger
authors.affiliation: Department of Chemistry and Biochemistry, Florida State University , Tallahassee, Florida 32306, United States.
authors.forename: T Gannon
authors.initials: TG
authors.lastname: Parker
authors.affiliation: Laboratorie de Physique et Chimie des Nano-objets, Institut National des Sciences Appliquées , 31077 Toulouse Cedex 4, France.
authors.forename: Laurent
authors.initials: L
authors.lastname: Maron
authors.affiliation: Department of Chemistry and Biochemistry, Florida State University , Tallahassee, Florida 32306, United States.
authors.forename: Thomas E
authors.initials: TE
authors.lastname: Albrecht-Schmitt