Plutonium compounds

Short description: Chemical compounds containing the element plutonium

Various oxidation states of plutonium in solution

Plutonium compounds are compounds containing the element plutonium (Pu). At room temperature, pure plutonium is silvery in color but gains a tarnish when oxidized.[1] The element displays four common ionic oxidation states in aqueous solution and one rare one:[2]

* Pu(III), as Pu3+ (blue lavender)
* Pu(IV), as Pu4+ (yellow brown)
* Pu(V), as PuO+2 (light pink)[note 1]
* Pu(VI), as PuO2+2 (pink orange)
* Pu(VII), as PuO3−5 (green)-the heptavalent ion is rare.

The color shown by plutonium solutions depends on both the oxidation state and the nature of the acid anion.[4] It is the acid anion that influences the degree of complexing—how atoms connect to a central atom—of the plutonium species. Additionally, the formal +2 oxidation state of plutonium is known in the complex [K(2.2.2-cryptand)] [PuIICp″3], Cp″ = C5H3(SiMe3)2.[5]

A +8 oxidation state has been reported as well in the volatile tetroxide PuO4.[6] Though it readily decomposes via a reduction mechanism similar to FeO4, it is stated that PuO4 can be stabilized in alkaline solutions, tetrachloromethane, and chloroform.[7][6] However, a more recent study showed that Pu(VIII) does not form in aqueous alkaline solutions.[8]

Metallic plutonium is produced by reacting plutonium tetrafluoride with barium, calcium or lithium at 1200 °C.[9] Metallic plutonium is attacked by acids, oxygen, and steam but not by alkalis and dissolves easily in concentrated hydrochloric, hydroiodic and perchloric acids.[10] Molten metal must be kept in a vacuum or an inert atmosphere to avoid reaction with air.[10] At 135 °C the metal will ignite in air and will explode if placed in carbon tetrachloride.[11]

Plutonium pyrophoricity can cause it to look like a glowing ember under certain conditions. Twenty micrograms of pure plutonium hydroxide

Plutonium is a reactive metal. In moist air or moist argon, the metal oxidizes rapidly, producing a mixture of oxides and hydrides.[12] If the metal is exposed long enough to a limited amount of water vapor, a powdery surface coating of PuO2 is formed.[12] Also formed is plutonium hydride but an excess of water vapor forms only PuO2.[10]

Plutonium shows enormous, and reversible, reaction rates with pure hydrogen, forming plutonium hydride.[13] It also reacts readily with oxygen, forming PuO and PuO2 as well as intermediate oxides; plutonium oxide fills 40% more volume than plutonium metal. The metal reacts with the halogens, see below. The following oxyhalides are observed: PuOF, PuOCl, PuOBr, and PuOI. It will react with carbon to form PuC, nitrogen to form PuN, and silicon to form PuSi2.[2][11]

The organometallic chemistry of plutonium complexes is typical for organoactinide species; a characteristic example of an organoplutonium compound is plutonocene.[14][15] Computational chemistry methods indicate an enhanced covalent character in the plutonium-ligand bonding.[13][15]

Powders of plutonium, its hydrides and certain oxides like Pu2O3 are pyrophoric, meaning they can ignite spontaneously at ambient temperature and are therefore handled in an inert, dry atmosphere of nitrogen or argon. Bulk plutonium ignites only when heated above 400 °C. Pu2O3 spontaneously heats up and transforms into PuO2, which is stable in dry air, but reacts with water vapor when heated.[16]

Crucibles used to contain plutonium need to be able to withstand its strongly reducing properties. Refractory metals such as tantalum and tungsten along with the more stable oxides, borides, carbides, nitrides and silicides can tolerate this. Melting in an electric arc furnace can be used to produce small ingots of the metal without the need for a crucible.[10]

Cerium is used as a chemical simulant of plutonium for development of containment, extraction, and other technologies.[17]

## Contents

* 1 Halides
* 1.1 Fluorides
* 1.2 Chlorides
* 1.3 Bromides
* 1.4 Iodides
* 2 See also
* 3 Notes
* 4 References

## Halides

Plutonium reacts readily with halogens, forming halides of composition PuX3 (X=F, Cl, Br, I) or PuX4 (X=F).[2][11] The higher plutonium fluorides PuF
5 and PuF
6 and the higher plutonium chloride PuCl
4 are also known, though PuF
5 and PuCl
4 are only known in the gas phase. Several of these compounds form hydrates, with compositions PuF
3 * 0.40H2O, PuF
3 * 0.75H2O, PuF
4 * 2.5H2O, PuCl
3 * 3H2O, PuCl
3 * 6H2O, and PuBr
3 * 6H2O.[18]

### Fluorides

The compounds PuF
3, PuF
4, and PuF
6 are well-characterized. The plutonium(III) fluoride hydrate PuF
3 * 0.75H2O can be prepared from adding hydrofluoric acid to a plutonium(III) solution in nitric acid, from which it precipitates.[19] The hydrate can then be converted to the anhydrous form by heating in hydrofluoric acid stream.[18] However, this method for PuF
3 production is not favored as it can lead to problems with filtration after the product is precipitated. Alternatively, it can be produced by reacting plutonium compounds, such as PuO
2 or Pu
2(C

3 with gaseous fluorinating agents, such as HF, F
2, NF
3, ClF
3, or CCl

2. This method also produces other plutonium fluorides, but these can be reduced to the trifluoride by action of reducing agents such as hydrogen gas.[20] Due to the toxicity of these fluorinating agents, other methods have also been proposed, such as the reaction of plutonium dioxide with ammonium bifluoride.[21] PuF
3 is used to prepare plutonium metal, forming the metal on action by calcium and iodine.[22]

As with PuF
3, a plutonium(IV) fluoride (PuF
4) hydrate, PuF
4 * 2.5H2O, can be precipitated by hydrofluoric acid in aqueous solution. Surprisingly, however, decomposition of this compound in vacuum yields PuF
3 instead of PuF
4. Like with PuF
3, though, it can be converted to PuF
4 by heating in a stream of HF. It is most commonly produced by reacting plutonium dioxide with hydrofluoric acid at high temperatures with oxygen gas. Several other materials can be used in place of plutonium dioxide, like plutonium(IV) nitrate or plutonium peroxide.[18] Anhydrous PuF
4 adopts a polymeric structure, isostructural with uranium tetrafluoride. In addition to the anhydrous form, two distinct hydrates of PuF
4 are known: the aforementioned PuF
4 * 2.5H2O, and PuF
4 * xH
2O (0.5 ≤ x ≤ 2.0). The hydrates are also isostructural to the corresponding uranium compounds. PuF
4 * xH
2O (0.5 ≤ x ≤ 2.0) adopts a cubic structure, while PuF
4 * 2.5H2O adopts an orthorhombic structure.[23] PuF
4 has been found to slowly age over time; a 30 year old sample of PuF
4 was found to contain 88% anhydrous PuF
4, 8% PuF
4 * 1.6H2O, and 4% PuO
2.[24] It is an important intermediate in plutonium metal production.[23]

Upon reaction with fluorine gas at high temperatures, PuF
4 is oxidized to plutonium hexafluoride, PuF
6. It is also readily produced upon reaction with powerful fluorinating agents, like krypton difluoride and dioxygen difluoride.[18] Unlike the related compound uranium hexafluoride, PuF
6 is unstable and highly reactive.[25] PuF
6 solid is prone to radiolysis from alpha particles produced in the radioactive decay of plutonium, forming PuF
4 and fluorine gas; however, gas phase reaches a stable equilibrium.[26][27] It undergoes slow hydrolysis to plutonyl fluoride PuO

2. In hydrofluoric acid solution, PuO

2 forms a hydrate, PuO

2 * H2O, and a solid incorporating HF, PuO

2 * HF * 4H2O.[18]

Plutonium also forms a few fluorides intermediate between PuF
4 and PuF
6, namely plutonium(V) fluoride PuF
5, as well as the mixed-valent Pu

17. Pu

17 is a brick-red solid formed during the production of PuF
6. PuF
5 is a weakly-characterized compound only known in the gas phase.[18]

### Chlorides

The only stable binary plutonium chloride in the solid phase is plutonium(III) chloride, PuCl
3. It can be produced in several ways. For medium-scale reactions (between 1 and 10 grams), the best method of PuCl
3 production is the action of hydrochloric acid on plutonium(III) oxalate.[18] Plutonium(III) oxalate can also be converted to plutonium(III) chloride by action of hexachloropropene.[28] Analytically pure samples of PuCl
3 can be created by reacting plutonium(IV) oxide prepared by calcination of plutonium(IV) oxalate with phosgene or carbon tetrachloride at elevated temperatures (>500 °C). PuCl
3 has been determined to adopt the uranium(III) chloride-type structure. In addition to anhydrous PuCl
3, multiple hydrates are also known, with compositions PuCl
3 * 3H2O and PuCl
3 * 6H2O.[18][29] PuCl
3 * 6H2O, which can be synthesized by evaporating HCl solutions,[18] adopts the GdCl
3 * 6H2O-type structure,[note 2] consisting of PuCl
2(H
2O)+
6 cations which are linked by chloride anions.[31] It melts in its own waters of crystallization at 94 °C.[32] PuCl
3 * 3H2O is isostructural with NdCl
3 * 3H2O.[29]

While it does not exist as a solid, dissociating into plutonium(III) chloride and chlorine gas, binary plutonium tetrachloride is known in the gas phase,[30] and it forms several stable adducts, such as with dimethoxyethane[33] or diphenylsulfoxide.[34] Plutonium tetrachloride gas is formed from the reaction of plutonium(III) chloride with chlorine gas at high temperatures, enhancing the volatility of the product.[18]: 1094 The dimethoxyethane adduct, PuCl
4(DME)
2 (DME=dimethoxyethane), can be prepared by evaporating a plutonium(IV) solution in HCl, adding the residue to a solution of DME, and then adding (CH

3SiCl.[33] This adduct can be used to prepare other compounds. For example, when it is dissolved in tetrahydrofuran, it forms the mixed-valence complex [PuIII

2(thf)
5]+[PuIV

5(thf)]− (THF=tetrahydrofuran).[35]

Despite solid PuCl
4 being unknown, several stable solid plutonium(IV) chlorides derived from PuCl
4, such as the hexachloroplutonates, are well-characterized.[18] The hexachloroplutonate ion (PuCl2−
6) is the dominant plutonium species in concentrated hydrochloric acid, and several compounds are known containing this ion. Dicaesium hexachloroplutonate (Cs
2PuCl
6) can be precipitated from concentrated HCl solution by the addition of caesium chloride.[36] Cs
2PuCl
6 can be used to prepare other plutonium compounds, such as the cyclopentadienide complex (η5−C

3PuCl. Other hexachloroplutonates are also known, such as K
2PuCl
6, Rb
2PuCl
6, (N(CH

2PuCl
6, and (N(C

2PuCl
6.[18]

### Bromides

The only stable compound in the plutonium-bromine system is PuBr3. It is formed via several methods, the two best ones being direct synthesis from plutonium and bromine, and reaction of plutonium hydride with hydrobromic acid. It is also prepared by the hydrobromination of various plutonium compounds, like Pu
2(C

3, PuCl
3, and PuBr
3 * 6H2O, vacuum decomposition of PuBr
3 * 6H2O, or reaction of Pu(OH)
4 with bromine. Its structure, termed the PuBr
3 structure, consists of PuBr
8 polyhedra, where plutonium has a coordination geometry of bicapped trigonal prismatic, which link together to form infinite chains.[18] A hydrate of plutonium(III) bromide, PuBr
3 * 6H2O, is also known, and is formed from plutonium bromide solutions containing water. Its structure consists of the complex [PuBr
2(H
2O)
6]+
, and is isostructural with GdCl
3 * 6H2O.[37][38] It also forms a complex with tetrahydrofuran, PuBr
3(THF)
4 (THF=tetrahydrofuran), which can be formed by reacting plutonium and bromine in THF solution, though the hexahydrate is formed if water is present in the THF solution.[37] The THF complex is used in the synthesis of other plutonium compounds.[39]

A few plutonium bromide complexes are known containing plutonium(IV). Plutonium tetrabromide forms stable complexes with hexamethylphosphoramide (PuBr
4 * 2[(CH

2N]
3PO) triphenylphosphine oxide (PuBr
4 * 2(C

3PO),[40] and tricyclohexylphosphine oxide (PuBr
4 * 2(C

11)
3PO),[41] as well as an unstable complex with acetonitrile (PuBr
4 * 4CH
3CN), which decomposes to a plutonium(III) compound.[40] The plutonium(IV) complex ion PuBr2−
6 is also known, found in the tetraethylammonium salt [(C

4N]
2PuBr
6.[42][18]

### Iodides

Plutonium(III) iodide can be prepared by reacting plutonium metal with either hydroiodic acid or mercury(II) iodide. It is extremely moisture-sensitive, and when even traces of water are present in its formation conditions, plutonium oxyiodide, PuOI, is formed instead. It adopts the PuBr
3-type structure. Several plutonium triiodide complexes are known, such as PuI
3(THF)
4 (THF=tetrahydrofuran), PuI
3(DMSO)
4 (DMSO=dimethylsulfoxide), and PuI
3(py)
4 (py=pyridine). These complexes can be formed by reacting plutonium metal with iodine in tetrahydrofuran, dimethylsulfoxide, or pyridine solutions, respectively. PuI
3 is a poorly characterized solid.[18]

## See also

* Uranium compounds
* Neptunium compounds
* Americium compounds
* Samarium compounds

## Notes

1. ↑ The PuO+2 ion is unstable in solution and will disproportionate into Pu4+ and PuO2+2; the Pu4+ will then oxidize the remaining PuO+2 to PuO2+2, being reduced in turn to Pu3+. Thus, aqueous solutions of PuO+2 tend over time towards a mixture of Pu3+ and PuO2+2. UO+2 is unstable for the same reason.[3]
2. ↑ PuCl
3 * 6H2O is known to be isostructural with SmCl
3 * 6H2O,[30] which adopts the GdCl
3 * 6H2O-type structure.[31]

## References

1. ↑ Heiserman, David L. (1992). "Element 94: Plutonium". Exploring Chemical Elements and their Compounds. New York (NY): TAB Books. pp. 339. ISBN 0-8306-3018-X. https://archive.org/details/exploringchemica01heis.
2. ↑ 2.0 2.1 2.2 Lide, David R., ed (2006). Handbook of Chemistry and Physics (87th ed.). Boca Raton: CRC Press, Taylor & Francis Group. pp. 4–27. ISBN 0-8493-0487-3.
3. ↑ Crooks, William J. (2002). "Nuclear Criticality Safety Engineering Training Module 10 – Criticality Safety in Material Processing Operations, Part 1". http://ncsp.llnl.gov/ncset/Module10.pdf.
4. ↑ Matlack, George (2002). A Plutonium Primer: An Introduction to Plutonium Chemistry and its Radioactivity. Los Alamos National Laboratory. LA-UR-02-6594.
5. ↑ Windorff, Cory J.; Chen, Guo P; Cross, Justin N; Evans, William J.; Furche, Filipp; Gaunt, Andrew J.; Janicke, Michael T.; Kozimor, Stosh A. et al. (2017). "Identification of the Formal +2 Oxidation State of Plutonium: Synthesis and Characterization of {PuII[C5H3(SiMe3)2]3}−". J. Am. Chem. Soc. 139 (11): 3970–3973. doi:10.1021/jacs.7b00706. PMID 28235179.
6. ↑ 6.0 6.1 Zaitsevskii, Andréi; Mosyagin, Nikolai S.; Titov, Anatoly V.; Kiselev, Yuri M. (21 July 2013). "Relativistic density functional theory modeling of plutonium and americium higher oxide molecules". The Journal of Chemical Physics 139 (3): 034307. doi:10.1063/1.4813284. PMID 23883027. Bibcode: 2013JChPh.139c4307Z.
7. ↑ Kiselev, Yu. M.; Nikonov, M. V.; Dolzhenko, V. D.; Ermilov, A. Yu.; Tananaev, I. G.; Myasoedov, B. F. (17 January 2014). "On existence and properties of plutonium(VIII) derivatives". Radiochimica Acta 102 (3): 227–237. doi:10.1515/ract-2014-2146.
8. ↑ Fedosseev, Alexander M.; Bessonov, Alexi A.; Shilov, Vladimir P. (September 5, 2022). "Is octavalent plutonium really formed during oxidation in alkaline aqueous solutions?". Radiochimica Acta 110 (12): 955–959. doi:10.1515/ract-2022-0056.
9. ↑ Eagleson, Mary (1994). Concise Encyclopedia Chemistry. Berlin: Walter de Gruyter. p. 840. ISBN 978-3-11-011451-5. https://archive.org/details/conciseencyclope00eagl.
10. ↑ 10.0 10.1 10.2 10.3 Miner, William N.; Schonfeld, Fred W. (1968). "Plutonium". in Clifford A. Hampel. The Encyclopedia of the Chemical Elements. New York (NY): Reinhold Book Corporation. pp. 540–546. https://archive.org/details/encyclopediaofch00hamp.
11. ↑ 11.0 11.1 11.2 Emsley, John (2001). "Plutonium". Nature's Building Blocks: An A–Z Guide to the Elements. Oxford (UK): Oxford University Press. pp. 324–329. ISBN 0-19-850340-7.
12. ↑ 12.0 12.1 "Plutonium, Radioactive". Wireless Information System for Emergency Responders (WISER). Bethesda (MD): U.S. National Library of Medicine, National Institutes of Health. http://webwiser.nlm.nih.gov/getSubstanceData.do;jsessionid=89B673C34252C77B4C276F2B2D0E4260?substanceID=419&displaySubstanceName=Plutonium, Radioactive&UNNAID=&STCCID=&selectedDataMenuItemID=44. (public domain text)
13. ↑ 13.0 13.1 Hecker, Siegfried S. (2000). "Plutonium and its alloys: from atoms to microstructure". Los Alamos Science 26: 290–335. https://fas.org/sgp/othergov/doe/lanl/pubs/00818035.pdf. Retrieved February 15, 2009.
14. ↑ Greenwood, N. N.; Earnshaw, A. (1997). Chemistry of the Elements (2nd ed.). Oxford (UK): Butterworth-Heinemann. p. 1259. ISBN 0-7506-3365-4.
15. ↑ 15.0 15.1 Apostolidis, Christos; Walter, Olaf; Vogt, Jochen; Liebing, Phil; Maron, Laurent; Edelmann, Frank T. (2017). "A Structurally Characterized Organometallic Plutonium(IV) Complex" (in en). Angewandte Chemie International Edition 56 (18): 5066–5070. doi:10.1002/anie.201701858. ISSN 1521-3773. PMID 28371148. Bibcode: 2017ACIE...56.5066A.
16. ↑ "Primer on Spontaneous Heating and Pyrophoricity – Pyrophoric Metals – Plutonium". Washington (DC): U.S. Department of Energy, Office of Nuclear Safety, Quality Assurance and Environment. 1994. http://www.hss.energy.gov/NuclearSafety/techstds/standard/hdbk1081/hbk1081d.html#ZZ281.
17. ↑ Crooks, W. J. (2002). "Low Temperature Reaction of ReillexTM HPQ and Nitric Acid". Solvent Extraction and Ion Exchange 20 (4–5): 543–559. doi:10.1081/SEI-120014371. http://sti.srs.gov/fulltext/ms2000068/ms2000068.html. Retrieved January 24, 2010.
18. ↑ 18.00 18.01 18.02 18.03 18.04 18.05 18.06 18.07 18.08 18.09 18.10 18.11 18.12 18.13 18.14 Clark, David L.; Hecker, Siegfried S.; Jarvinen, Gordon D.; Neu, Mary P. (2011). "Plutonium". The Chemistry of the Actinide and Transactinide Elements. doi:10.1007/978-94-007-0211-0_7. ISBN 978-94-007-0211-0. https://www.xylenepower.com/THE_CHEMISTRY_OF_THE_ACTINIDE_AND_TRANSA.pdf.
19. ↑ Burney, G. A.; Tober, F. W. (1965). "Precipitation of Plutonium Trifluoride". Industrial & Engineering Chemistry Process Design and Development 4: 28–32. doi:10.1021/i260013a009. https://doi.org/10.1021/i260013a009.
20. ↑ Tosolin, A.; Souček, P.; Beneš, O.; Vigier, J.-F.; Luzzi, L.; Konings, R.J.M. (2018). "Synthesis of plutonium trifluoride by hydro-fluorination and novel thermodynamic data for the PuF3-LiF system". Journal of Nuclear Materials 503: 171–177. doi:10.1016/j.jnucmat.2018.02.037. https://doi.org/10.1016/j.jnucmat.2018.02.037.
21. ↑ Claux, Benoit; Beneš, Ondřej; Capelli, Elisa; Souček, Pavel; Meier, Roland (2016). "On the fluorination of plutonium dioxide by ammonium hydrogen fluoride". Journal of Fluorine Chemistry 183: 10–13. doi:10.1016/j.jfluchem.2015.12.009. Bibcode: 2016JFluC.183...10C.
22. ↑ "Preparation of Plutonium Metal by Calcium Reduction of Sodium Plutonium (IV) Fluoride". https://www.jstage.jst.go.jp/article/jnst1964/8/12/8_12_682/_pdf.
23. ↑ 23.0 23.1 Kinyon, Jared S.; Villa-Aleman, Eliel; Ciprian, Elodia; Hixon, Amy E.; Foley, Bryan J.; Christian, Jonathan H.; Darvin, Jason R.; Dick, Don D. et al. (2024). "Chemical and spectroscopic characterization of plutonium tetrafluoride". Dalton Transactions 53 (48): 19166–19178. doi:10.1039/D4DT02509A. PMID 39466681. https://doi.org/10.1039/D4DT02509A.
24. ↑ Wayne, David M.; Stritzinger, Jared T.; Casella, Amanda J.; Sweet, Lucas E.; Corbey, Jordan F.; Garcia, Daniel J.; Wylie, E. Miller; Tandon, Lav et al. (2021). "X-ray diffraction, differential scanning calorimetry and evolved gas analysis of aged plutonium tetrafluoride (PuF4)". Journal of Radioanalytical and Nuclear Chemistry 329 (2): 741–756. doi:10.1007/s10967-021-07810-z. http://doi.org/10.1007/s10967-021-07810-z.
25. ↑ Shigeo Tsujimura; Kenmei Hirano; Akira Takahashi; Ginji Fujisawa (September 1972). "Thermal Decomposition of Plutonium Hexafluoride". Journal of Nuclear Science and Technology 9 (9): 534–537. https://www.jstage.jst.go.jp/article/jnst1964/9/9/9_9_534/_pdf.
26. ↑ Weinstock, Bernard; Malm, John G. (1956). "The properties of plutonium hexafluoride". Journal of Inorganic and Nuclear Chemistry 2 (5–6): 380–394. doi:10.1016/0022-1902(56)80092-4. https://doi.org/10.1016/0022-1902(56)80092-4.
27. ↑ "Laboratory investigations in support of fluid-bed fluoride volatility processes - Part VII. The Decomposition of Gaseous Plutonium Hexafluoride". https://www.osti.gov/servlets/purl/4628896/4628896.pdf.
28. ↑ "Preview". https://inis.iaea.org/records/h3p87-hyf93/preview/53064563.pdf.
29. ↑ 29.0 29.1 "Synthesis of actinide chlorides for molten salt preparation". https://airdrive.eventsair.com/eventsairseasiaprod/production-ausimm-public/ab4ca63977fa48b5b15a71d641db7c1f.
30. ↑ 30.0 30.1 Lemire, R. J. et al., Chemical Thermodynamics of Neptunium and Plutonium, Elsevier, Amsterdam, 2001.
31. ↑ 31.0 31.1 Kandabadage, Thimira; Legnon, Beau; Baranets, Sviatoslav (2024). "Comprehensive structural study of lanthanide(III) chloride hydrates: [ RE Cl3· x H2O ( RE = La–Nd, Sm–Lu; x = 6, 7)]". Acta Crystallographica Section E: Crystallographic Communications 80 (12): 1342–1349. doi:10.1107/S2056989024011319. PMID 39906789. PMC 11789172. Bibcode: 2024AcCrE..80.1342K. https://doi.org/10.1107/S2056989024011319.
32. ↑ Brown, David (1972). "Compounds with Chlorine". Transurane. pp. 129–147. doi:10.1007/978-3-662-11547-3_7. ISBN 978-3-662-11548-0. https://doi.org/10.1007/978-3-662-11547-3_7.
33. ↑ 33.0 33.1 Reilly, Sean D.; Brown, Jessie L.; Scott, Brian L.; Gaunt, Andrew J. (2014). "Synthesis and characterization of NPCL4(DME)2and PuCl4(DME)2neutral transuranic An(iv) starting materials". Dalton Trans 43 (4): 1498–1501. doi:10.1039/C3DT53058B. PMID 24285347. https://doi.org/10.1039/C3DT53058B.
34. ↑ Cary, Samantha K.; Boland, Kevin S.; Cross, Justin N.; Kozimor, Stosh A.; Scott, Brian L. (2017). "Advances in containment methods and plutonium recovery strategies that led to the structural characterization of plutonium(IV) tetrachloride tris-diphenylsulfoxide, PuCl4(OSPh2)3". Polyhedron 126: 220–226. doi:10.1016/j.poly.2017.01.013. https://doi.org/10.1016/j.poly.2017.01.013.
35. ↑ Pattenaude, Scott A.; Anderson, Nickolas H.; Bart, Suzanne C.; Gaunt, Andrew J.; Scott, Brian L. (2018). "Non-aqueous neptunium and plutonium redox behaviour in THF – access to a rare Np(III) synthetic precursor". Chemical Communications 54 (48): 6113–6116. doi:10.1039/C8CC02611D. PMID 29736543. https://doi.org/10.1039/C8CC02611D.
36. ↑ Wang, Yufei; Rice, Natalie T.; Knapp, Julia G.; Adelman, Sara L.; Aldrich, Kelly E.; Arko, Brian T.; Besmer, Manuel L.; Gilhula, J. Connor et al. (2025). "Insights for controlling plutonium behavior in hydrochloric acid solutions". Inorganic Chemistry Frontiers 12 (14): 4392–4408. doi:10.1039/D5QI00409H. https://pubs.rsc.org/en/content/articlelanding/2025/qi/d5qi00409h.
37. ↑ 37.0 37.1 Gaunt, Andrew J.; Reilly, Sean D.; Enriquez, Alejandro E.; Hayton, Trevor W.; Boncella, James M.; Scott, Brian L.; Neu, Mary P. (2008). "Low-Valent Molecular Plutonium Halide Complexes". Inorganic Chemistry 47 (18): 8412–8419. doi:10.1021/ic8009139. PMID 18714989. https://doi.org/10.1021/ic8009139.
38. ↑ "[PuBr2(H2O)6[Br] (PuBr3[H2O]6, T = 141(2) K) Crystal Structure"]. Springer Materials. https://materials.springer.com/isp/crystallographic/docs/sd_1124041.
39. ↑ Galley, Shane S.; Pattenaude, Scott A.; Ray, Debmalya; Gaggioli, Carlo Alberto; Whitefoot, Megan A.; Qiao, Yusen; Higgins, Robert F.; Nelson, W. L. et al. (2021). "Using Redox-Active Ligands to Generate Actinide Ligand Radical Species". Inorganic Chemistry 60 (20): 15242–15252. doi:10.1021/acs.inorgchem.1c01766. PMID 34569783. https://doi.org/10.1021/acs.inorgchem.1c01766.
40. ↑ 40.0 40.1 Brown, D.; Holah, D. G.; Rickard, C. E. F. (1968). "The stabilisation of plutonium tetrabromide and uranium pentabromide". Chemical Communications (11): 651. doi:10.1039/C19680000651. https://doi.org/10.1039/C19680000651.
41. ↑ Windorff, Cory J.; Goodwin, Conrad A. P.; Sperling, Joseph M.; Albrecht-Schönzart, Thomas E.; Bai, Zhuanling; Evans, William J.; Huffman, Zachary K.; Jeannin, Renaud et al. (2023). "Stabilization of Pu(IV) in PuBr4(OPCy3)2 and Comparisons with Structurally Similar THX4(OPR3)2 (R = Cy, Ph) Molecules". Inorganic Chemistry 62 (44): 18136–18149. doi:10.1021/acs.inorgchem.3c02575. PMID 37875401. https://doi.org/10.1021/acs.inorgchem.3c02575.
42. ↑ Ryan, J.L.; Jørgensen, Chr. Klixbüll (1964). "Electron transfer and 5f→6f transitions in uranium(IV), neptunium(IV), plutonium(IV) hexahalides". Molecular Physics 7 (1): 17–29. doi:10.1080/00268976300100781. Bibcode: 1964MolPh...7...17R. https://doi.org/10.1080/00268976300100781.

* v
* t
* e

Plutonium compounds

Plutonium(II)|

* PuH2
* PuB2

Plutonium(III)|

* PuH3
* PuB
* PuCl3
* PuF3

Plutonium(IV)|

* PuC
* PuF4
* PuO2
* Pu(C8H8)2

Plutonium(VI)|

* PuF6

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Original source: https://en.wikipedia.org/wiki/Plutonium compounds. Read more

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