High-Yield Synthesis and Single-Crystal X-ray Structure of a Plutonium(III) Aquo Complex:  [Pu(H2O)9][CF3SO3]3

Matonic, John H.; Scott, Brian L.; Neu, Mary P.

doi:10.1021/ic015509p

Cited by 80 publications

(82 citation statements)

References 12 publications

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“…[4][5][6][7][8][9][10][11][12][13][14] Exploration of this field is filled with opportunity as there are only a few systems that have systematically spanned the lanthanide and actinide series such as the aquo-triflates, phosphonates, and phosphites. [15][16][17][18][19][20][21][22][23][24][25] It is in this objective we have chosen to explore the rare earth molybdates.…”

Section: Introductionmentioning

confidence: 99%

From Yellow to Black: Dramatic Changes between Cerium(IV) and Plutonium(IV) Molybdates

et al. 2013

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Section: Introductionmentioning

confidence: 99%

From Yellow to Black: Dramatic Changes between Cerium(IV) and Plutonium(IV) Molybdates

et al. 2013

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“…The conversion of UO 3 to UF 6 is not an efficient process, so the oxide is reduced at high temperatures by H 2 . The resulting UO 2 is treated with HF to give UF 4 , commonly known as 'green salt'. A reaction between UF 4 and gaseous F 2 is the final step in the conversion process and yields nearly quantitatively gaseous UF 6 .…”

Section: Nuclear Fuel Cyclementioning

confidence: 99%

“…In transition metal dioxo complexes, MO 2 L x , the oxo ligand geometry (cis or trans) is almost entirely dependent on the electron count. For ReO 2 (CH 3 ) 3 (d 0 system) (17), the oxo ligands are cis in order to maximize the π -bonding, while the oxo ligands in ReO 2 (py) 4 (d 2 system) (18) are found in a trans geometry to minimize electronic repulsions with the unpaired metal-based electrons residing in the equatorial dx 2 -y 2 orbital. As a result of this disparity, many questions on the structure and bonding of the actinides center on the role of the 5f-electrons.…”

Section: Molecular Orbital Descriptions -The Linear Dioxo Diagrammentioning

confidence: 99%

“…It should be noted that in all of these compounds the remainder of the coordination sphere is made up of bound H 2 O molecules. The end member of the speciation is the neutral An(OH) 4 or AnO 2 ·2H 2 O. This complex has low solubility but has been postulated to exist in solutions from solubility experiments when using the isolated solid as the starting material.…”

Section: Tetravalent the Anmentioning

confidence: 99%

“…Monomeric anions of the form, AnO 2 (OH) x 2− (x = 4, 5) have been identified to be in equilibrium with each other, and, as for the uranium analog, the neptunyl tetrahydroxide has been crystallographically characterized by addition of [Co(NH 3 ) 6 ] 3+ to alkaline solutions. The bond lengths for the AnO 2 (OH) 4 2− have been established by both single-crystal X-ray diffraction studies and XAFS. The average An=O (14).…”

Section: Tetravalent the Anmentioning

confidence: 99%

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Actinides: Inorganic & Coordination ChemistryBased in part on the article Actinides: Inorganic & Coordination Chemistry by Grigorii L. Soloveichik which appeared in the Encyclopedia of Inorganic Chemistry, First Edition .

Keogh¹

2005

Encyclopedia of Inorganic Chemistry

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The Inorganic and Coordination Chemistry of the 5f elements (Actinides) is intermediate between that of the transition metals and the 4f elements (Lanthanides). The first four members of the actinide series, Ac, Th, Pa, and U, are all naturally occurring but have unstable nuclei, making them radioactive. The other elements in the actinide series (transuranium elements or transuranics) are also radioactive and have been made by man through a variety of nuclear transformation processes, for example, neutron irradiation, atom bombardment, and radioactive decay. The actinide series may be broken into two separate groups, the light or early actinides (Ac–Am) and the heavy or late actinides (Cm–Lr). The chemical behaviors of these two groups are distinct. The light actinides are capable of being stabilized in a variety of oxidation states, for example, II to VII, and have been found to exhibit a significant degree of covalency in binding ligands. The heavy actinides are more reminiscent of the lanthanides in that the most persistent oxidation state is the trivalent and the bonding predominately occurs through ionic interactions. This difference has led to a substantial number of studies into the role of the 5f orbitals in structure and bonding of the actinides. One of the ions that has received a great deal of attention is the ubiquitous actinyl ion, AnO22+/+. This ion is the stable form for all aqueous complexes of the pentavalent and hexavalent light actinides. The oxo ligands are always found in a trans geometry and are strongly bound (triple bond) through a combination of σ‐ and π‐bonds with the 5f and 6d orbitals of the actinide metal center. While these strong covalent interactions exist with the axial oxo ligands, the bonding within the equatorial plane is primarily based on ionic interactions. The ability of the light actinides to access multiple oxidation states leads to rich and, sometimes, complex electrochemistry. For example, under acidic conditions the reduction potentials for PuO 2 2+ , PuO 2 + , Pu 4+ , and Pu 3+ are all close to 1 V. The physical manifestation of these close reduction potentials is an aqueous solution in which the plutonium can exist in four different oxidation states simultaneously. By careful control of the conditions, oxidation state pure solutions can be obtained for quantitative and qualitative studies. The binding affinities of the actinide ions to ligands follow the general trend An 4+ > An 3+ ∼ AnO 2 2+ ≫ AnO 2 + . Since the actinides are strong acids, the ions preferentially bond strong bases, for example, halides, oxygen donors, and so on. Owing to the greater degree of covalency in actinide complexes compared to the lanthanides, complexes with ligands having nitrogen, phosphorus, sulfur, and selenium donors are also found.

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Plutonium: Radionuclides

Neu¹,

Goff²,

Runde³

2005

Encyclopedia of Inorganic Chemistry

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Plutonium is the most debated actinide element because of its dual use in devastating nuclear weapons and beneficial generation of nuclear energy. Plutonium metal exists in several allotropic phases and plutonium in solution exhibits a rich and complex chemistry. The ability to exist in up to four oxidation states makes plutonium unique among all elements. Pu(III) and Pu(VI) form only under reducing or oxidizing conditions, respectively; whereas Pu(IV) and Pu(V) have broad stability ranges within the geochemical bounds of environmental systems. When Pu(IV) is above trace concentration and particulate matter is present, then solids or suspended colloids are the predominant chemical forms. In contrast, Pu(V), as PuO $_{2}^{+}$ , has relatively higher solubility as an aquo species or a monomeric complex of natural ligands (hydroxide, chloride, sulfate, etc.). Stronger complexing, polydentate ligands, such as carbonate and organics, tend to increase plutonium solubility by forming very stable Pu(IV) complexes. Minerals, high molecular weight organic matter, and bacteria can either increase or decrease the solubility of plutonium, depending upon their chemical properties, mechanisms of interaction, and the geochemical conditions of the surrounding environment. Plutonium generally has very low solubility, low mobility, and few health consequences from environmental forms, and therefore poses little risk to living systems under nearly all conditions. This article provides a brief overview of the chemistry and behavior of plutonium in aqueous solutions and in the environment.

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High-Yield Synthesis and Single-Crystal X-ray Structure of a Plutonium(III) Aquo Complex: [Pu(H₂O)₉][CF₃SO₃]₃

Cited by 80 publications

References 12 publications

From Yellow to Black: Dramatic Changes between Cerium(IV) and Plutonium(IV) Molybdates

From Yellow to Black: Dramatic Changes between Cerium(IV) and Plutonium(IV) Molybdates

Actinides: Inorganic & Coordination ChemistryBased in part on the article Actinides: Inorganic & Coordination Chemistry by Grigorii L. Soloveichik which appeared in the Encyclopedia of Inorganic Chemistry, First Edition .

Plutonium: Radionuclides

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