User:UnbihexiumFan/Plutonium(III) bromide

UnbihexiumFan/Plutonium(III) bromide
Names
	IUPAC name Plutonium(III) bromide
	Other names Plutonium tribromide
Identifiers
CAS Number	15752-46-2; 20737-00-2 (hexahydrate);
3D model (JSmol)	Interactive image;
ChemSpider	129557993;
	InChI InChI=1S/3BrH.Pu/h3*1H;/q;;;+3/p-3 Key: ZOUHELNKIRPXTH-UHFFFAOYSA-K;
	SMILES [Br-].[Br-].[Br-].[Pu+3];
Properties
Chemical formula	PuBr3
Molar mass	484 g·mol−1
Appearance	Green solid
Density	6.750 g/cm3
Melting point	Variously reported between 662 °C (1,224 °F; 935 K) and 767 °C (1,413 °F; 1,040 K)
Boiling point	1,300 °C (2,370 °F; 1,570 K) or greater
	Except where otherwise noted, data are given for materials in their standard state (at 25 °C [77 °F], 100 kPa). Infobox references

Plutonium(III) bromide is an inorganic salt of bromine and plutonium with the formula PuBr₃. This radioactive green solid has few uses, however its crystal structure is often used as a structural archetype in crystallography.

TODO: Expand lead

Synthesis

reaction of plutonium metal and bromine in a vacuum is the best method, but difficult due to poor availability of metals^[4]
bromination of dried plutonium(IV) hydroxide with hydrogen bromide (>600 C) or bromine and disulfur dibromide (>800 C)
reaction of plutonium(IV) oxalate and hydrogen bromide @ 500C
reaction of plutonium(III) bromide hexahydrate and hydrogen bromide @ 30-300 C (usually contaminated w/ plutonium oxybromide
- adding ammonium bromide minimizes contamination
plutonium(III) chloride reaction with hydrogen bromide @ 750C
plutonium(III) oxalate reaction with hydrogen bromide up to 600C
purified by vacuum sublimation at temperatures >850 C^[5]^: 1095^[4]
hydrobromination of plutonium(IV) oxide, plutonium(III) chloride, or plutonium(III) oxalate
plutonium(III) oxalate produces higher purity result and reaction is faster
treating hexahydrate in a stream of dry air @ 225
hexahydrate is formed when anhydrous form picks up water^[6]
reaction of plutonium metal with HBr^[7]
best methods are plutonium metal + bromine and plutonium hydride in a stream of HBR
dehydration of hexahydrate by controlled thermal decomposition in vacuum and hydrobromination of Pu(III) oxalate (HBr OR HBr/H2 mix) @ 400-600 C can be used because avoid working with metal (plutonium(III) oxalate easily made from aq soln)^[5]^: 1095

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Properties

Curie‐Weiss paramagnetism at high temperatures^[8]
Anhydrous is hygroscopic, transforms to hexahydrate
Water soluble^[6]
anhydrous is green
hexahydrate is blue^: 1084
only stable binary Pu bromide^: 1092

^[5]

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Structure

Anhydrous

Crystal structure

Unit cell

PuBr₃: Pu³⁺ Br^-

orthorhombic PuBr₃ structure
six Pu-Br bonds form a trigonal prism
two bromine atoms cap the faces (bicapped trigonal prismatic)
capped prisms stack with triangular bases 1to form infinite chains
related to the PuCl3 structure but PuCl3 has extra halogen atom^[5]^{: 1096–1097}

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Hexahydrate

8-coordinate^[9]
GdCl3 structure^[10]

TODO: find more info about structure

Reactions

Converts to dioxide at 100 °C under oxygen
converts under air at higher temp
readily reduced to metal with calcium
does not react with bromine^[6]
reacts with moisture to make hexahydrate
in thf reacts w/ Dipotassium cyclooctatetraenide to make K(THF)2Pu(C8H8)2^[5]^: 1100

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Complexes

With tetrahydrofuran

THF complex PuBr₃(thf)₄
formed by reacting plutonium metal and bromine in thf^[9]

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Uses

adding hydrogen bromide to a plutonium-containing sample can determine how much metal there is because of plutonium(III) bromide production
if plutonium is oxidized then less hydrogen is produced on hydrobromination
read more info from there^[7]

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As a precursor to other compounds

can be used to make organic compounds e.g. salts of 2,4,6,8-tetra-tert-butyl-1-oxo-1H-phenoxazine-9-olate (DOPO) by reaction of thf adduct with H(DOPO^q) to make Pu(DOPO^q)₂(DOPO^sq) (q=quinone, oxidized form, ligand=-1) (sq=semiquinone, partially reduced form, ligand=-2)^[11]
thf adduct also reacts with Na₂(dtp)*2h2o (dtp=2,3-di-1H-tetrazol-5-ylpyrazine) to make Na2[Pu(Hdtp)(dtp)2(H2O)4]$9H2O, which has been studied for its unique structure^[12]
hydrate reacts with tricyclohexyl phosphate in isopropyl alcohol to make PuBr₄[OPCy₃]₂^[13]

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References

1 2 Greenwood, N. N. (2001). Chemistry of the elements (2nd ed.). Boston, Mass. p. 1270. ISBN 0750633654.{{cite book}}: CS1 maint: location missing publisher (link)
1 2 3 https://www.webelements.com/compounds/plutonium/plutonium_tribromide.html
↑ Lemire, R. J. et al., Chemical Thermodynamics of Neptunium and Plutonium, Elsevier, Amsterdam, 2001.
1 2 https://link.springer.com/chapter/10.1007/978-3-662-11547-3_8
1 2 3 4 5 Clark, David L.; Hecker, Siegfried S.; Jarvinen, Gordon D.; Neu, Mary P. (2011). "Plutonium". The Chemistry of the Actinide and Transactinide Elements (PDF). doi:10.1007/978-94-007-0211-0_7. ISBN 978-94-007-0211-0.
1 2 3 https://sgp.fas.org/othergov/doe/lanl/lib-www/la-pubs/00350347.pdf
1 2 https://www.osti.gov/etdeweb/servlets/purl/20285957
↑ https://doi.org/10.1063/1.1681318
1 2 https://pubs.acs.org/doi/10.1021/ic8009139
↑ "[PuBr2(H2O)6][Br] (PuBr3[H2O]6, T = 141(2) K) Crystal Structure". Springer Materials.
↑ https://public.magnet.fsu.edu/AToth/NSF%20publication%20access/2021/11%20Newly%20Entered%20Pubs%20November%202021/2021%20cited/2021_Using%20Redox-Active%20Ligands.pdf
↑ https://pubs.rsc.org/en/content/articlepdf/2025/sc/d5sc01808k
↑ https://pure.manchester.ac.uk/ws/portalfiles/portal/278424654/AnX4_OPR3_R2_CJW.pdf

[Greenwood-1] 1 2 Greenwood, N. N. (2001). Chemistry of the elements (2nd ed.). Boston, Mass. p. 1270. ISBN 0750633654.{{cite book}}: CS1 maint: location missing publisher (link)

[WEl-2] 1 2 3 https://www.webelements.com/compounds/plutonium/plutonium_tribromide.html

[ChemTherm-3] Lemire, R. J. et al., Chemical Thermodynamics of Neptunium and Plutonium, Elsevier, Amsterdam, 2001.

[AnBr_overview-4] 1 2 https://link.springer.com/chapter/10.1007/978-3-662-11547-3_8

[PuBook-5] 1 2 3 4 5 Clark, David L.; Hecker, Siegfried S.; Jarvinen, Gordon D.; Neu, Mary P. (2011). "Plutonium". The Chemistry of the Actinide and Transactinide Elements (PDF). doi:10.1007/978-94-007-0211-0_7. ISBN 978-94-007-0211-0.

[Synthesis-6] 1 2 3 https://sgp.fas.org/othergov/doe/lanl/lib-www/la-pubs/00350347.pdf

[Metal_analysis-7] 1 2 https://www.osti.gov/etdeweb/servlets/purl/20285957

[Magnetism-8] ttps://doi.org/10.1063/1.1681318

[Complexes-9] 1 2 https://pubs.acs.org/doi/10.1021/ic8009139

[PuBr3*6H2O_Springer_Materials-10] "[PuBr2(H2O)6][Br] (PuBr3[H2O]6, T = 141(2) K) Crystal Structure". Springer Materials.

[Precursor1-11] ttps://public.magnet.fsu.edu/AToth/NSF%20publication%20access/2021/11%20Newly%20Entered%20Pubs%20November%202021/2021%20cited/2021_Using%20Redox-Active%20Ligands.pdf

[Precursor2-12] ttps://pubs.rsc.org/en/content/articlepdf/2025/sc/d5sc01808k

[Precursor3-13] ttps://pure.manchester.ac.uk/ws/portalfiles/portal/278424654/AnX4_OPR3_R2_CJW.pdf

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