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{{chembox {{chembox
| ImageFile = Neptunocene.png
| Verifiedfields =
⚫ | ImageFile1 = Neptunocene-from-xtal-3D-balls.png
| Watchedfields =
| verifiedrevid = | ImageSize1 = 120
⚫ | IUPACName = Bis(''η''<sup>8</sup>-cyclooctatetraenyl)neptunium(IV)
⚫ | ImageFileL1 = Neptunocene-from-xtal-3D-balls.png
⚫ | OtherNames = Neptunium cyclooctatetraenide<br>Np(COT)<sub>2</sub>
| ImageFileR1 =
⚫ | Section1 = {{Chembox Identifiers
| ImageFileL2 =
⚫ |CASNo_Ref = {{cascite|correct|CAS}}
| ImageFileR2 =
⚫ |CASNo = 154974-81-9
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⚫ |ChemSpiderID_Ref = {{chemspidercite|changed|chemspider}}
⚫ | IUPACName = Bis(η<sup>8</sup>-cyclooctatetraenyl)neptunium(IV)
|SMILES = c1=cc=cc=c1..c1=cc=cc=c1
⚫ | OtherNames = Neptunium cyclooctatetraenide<br>Np(COT)<sub>2</sub>
|StdInChI=1S/2C5H5.Np/c2*1-2-4-5-3-1;/h2*1-5H;/q2*-1;+2
⚫ |Section1={{Chembox Identifiers
|StdInChIKey = FXDJOXAJBKYPFW-UHFFFAOYSA-N
⚫ | CASNo_Ref = {{cascite|correct|??}}
⚫ }}
⚫ | CASNo =
⚫ | Section2 = {{Chembox Properties
⚫ | ChemSpiderID_Ref = {{chemspidercite|changed|chemspider}}
|C=16
| ChemSpiderID =
|H=16
| PubChem =
|Np=1
| SMILES = .11.11
|Appearance = dark brown crystals as a solid, yellow in dilute solution
⚫ }}
|Solubility = insoluble, does not react with water
⚫ |Section2={{Chembox Properties
|Solvent = chlorocarbons
| Formula = C<sub>16</sub>H<sub>16</sub>Np
|SolubleOther = sparingly soluble (''ca.'' 0.5 g/L)
| MolarMass =
⚫ }}
| Appearance =
⚫ | Section3 = {{Chembox Hazards
| Density =
|MainHazards = radiation hazard, pyrophoric
| MeltingPt =
⚫ }}
| BoilingPt =
| Solubility =
⚫ }}
⚫ |Section3={{Chembox Hazards
| MainHazards = ignites in air
| FlashPt =
| AutoignitionPt =
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'''Neptunocene''', Np(C<sub>8</sub>H<sub>8</sub>)<sub>2</sub>, is an organoneptunium compound composed of a ] atom ] between two ] (COT<sup>2-</sup>) rings. As a solid it has a dark brown/red colour but it appears yellow when dissolved in ], in which it is sparingly soluble.<ref name=":0">{{Cite journal|last=Karraker|first=David G.|last2=Stone|first2=John Austin.|last3=Jones|first3=Erwin Rudolph.|last4=Edelstein|first4=Norman.|date=1970|title=Bis(cyclooctatetraenyl)neptunium(IV) and bis(cyclooctatetraenyl)plutonium(IV)|url=https://pubs.acs.org/doi/abs/10.1021/ja00719a014|journal=Journal of the American Chemical Society|language=en|volume=92|issue=16|pages=4841–4845|doi=10.1021/ja00719a014|issn=0002-7863|access-date=2021-03-22|archive-date=2024-05-03|archive-url=https://web.archive.org/web/20240503013428/https://pubs.acs.org/doi/abs/10.1021/ja00719a014|url-status=live}}</ref><ref name=":1">{{Cite book|last=Greenwood|first=Norman N.|title=Chemistry of the Elements|last2=Earnshaw|first2=Alan|publisher=Butterworth-Heinemann|year=1997|isbn=9780750633659|edition=2nd|pages=1278–1280}}</ref><ref name=":2">{{Cite journal|last=Eisenberg|first=David C.|last2=Streitwieser|first2=Andrew|last3=Kot|first3=Wing K.|date=1990|title=Electron transfer in organouranium and transuranium systems|url=https://pubs.acs.org/doi/pdf/10.1021/ic00326a004|journal=Inorganic Chemistry|volume=29|issue=1|pages=10–14|doi=10.1021/ic00326a004|issn=0020-1669|access-date=2021-03-22|archive-date=2024-05-03|archive-url=https://web.archive.org/web/20240503013432/https://pubs.acs.org/doi/pdf/10.1021/ic00326a004|url-status=live}}</ref><ref name=":3">{{Cite journal|last=Ridder|first=D. J. A. De|last2=Rebizant|first2=J.|last3=Apostolidis|first3=C.|last4=Kanellakopulos|first4=B.|last5=Dornberger|first5=E.|date=1996|title=Bis(cyclooctatetraenyl)neptunium(IV)|url=https://onlinelibrary.wiley.com/doi/abs/10.1107/S0108270195013047|journal=Acta Crystallographica Section C|language=en|volume=52|issue=3|pages=597–600|doi=10.1107/S0108270195013047|issn=1600-5759|access-date=2021-03-22|archive-date=2021-06-12|archive-url=https://web.archive.org/web/20210612105101/https://onlinelibrary.wiley.com/doi/abs/10.1107/S0108270195013047|url-status=live}}</ref><ref name="Yoshida750">{{cite book|last1=Yoshida|first1=Zenko|url=http://radchem.nevada.edu/classes/rdch710/files/neptunium.pdf|title=The Chemistry of the Actinide and Transactinide Elements|last2=Johnson|first2=Stephen G.|last3=Kimura|first3=Takaumi|last4=Krsul|first4=John R.|date=2006|publisher=Springer|editor1-last=Morss|editor1-first=Lester R.|edition=3rd|volume=3|location=Dordrecht, the Netherlands|pages=699–812|contribution=Neptunium|doi=10.1007/1-4020-3598-5_6|ref=Yoshida et al.|editor2-last=Edelstein|editor2-first=Norman M.|editor3-last=Fuger|editor3-first=Jean|access-date=2016-08-07|archive-date=2018-01-17|archive-url=https://web.archive.org/web/20180117190715/http://radchem.nevada.edu/classes/rdch710/files/neptunium.pdf|url-status=dead}}</ref> The compound is quite ].<ref name=":0" /><ref name=":1" /><ref name="Yoshida750" />
'''Neptunocene''', Np(C<sub>8</sub>H<sub>8</sub>)<sub>2</sub>, is an organoneptunium compound composed of a ] atom sandwiched between two ] rings. It was one of the first organoneptunium compounds to be synthesized. Neptunocene, a member of the "]s," a group of ]s incorporating ] from the ] series.


It was one of the first organoneptunium compounds to be synthesised, and is a member of the ] family of ]-based ]s.<ref name=":1" />
== Property and synthesis ==

It was synthesized in 1970 by reacting ] with ]. It is ] to ] and ], and they behave chemically identically: all three compounds are insensitive to water or dilute bases but are sensitive to air, reacting quickly to form oxides, and are only slightly soluble in ] and ].<ref name=Yoshida750>Yoshida et al., pp. 750–2</ref>
== Structure ==
The sandwich structure of neptunocene has been determined by ].<ref name=":3" /> The COT<sup>2-</sup> rings are found to be planar with 8 equivalent C–C bonds of 1.385 Å length, and sit parallel in an eclipsed conformation. The Np–COT distance (to the ring centroid) is 1.909 Å and the individual Np–C distances are 2.630 Å.<ref name=":3" />

Neptunocene assumes a ] crystal structure (''P''2<sub>1</sub>/''n'' ]) which is ] to ] and ] but not to ].<ref name=":3" />

== Synthesis and properties ==
Neptunocene was first synthesised in 1970 by reacting ] (NpCl<sub>4</sub>) with ] (K<sub>2</sub>(C<sub>8</sub>H<sub>8</sub>)) in ] or ]:<ref name=":0" />

: NpCl<sub>4</sub> + 2 K<sub>2</sub>(C<sub>8</sub>H<sub>8</sub>) → Np(C<sub>8</sub>H<sub>8</sub>)<sub>2</sub> + 4 KCl

The same reaction conditions have been routinely reproduced since then for the synthesis of the compound.<ref name=":2" /><ref name=":3" />

The three actinocenes ], neptunocene, and ] share virtually identical chemistry: they do not react in the presence of water or dilute base, but are very air-sensitive, quickly forming oxides.<ref name=":0" /><ref name=":1" /><ref name=":2" /> All three are only slightly soluble (up to about 10<sup>−3</sup> M concentrations) in aromatic or chlorinated solvents such as ], ], ] or ].<ref name=":0" /><ref name=":1" /><ref name=":3" /><ref name="Yoshida750" />


==References== ==References==
{{reflist}} {{reflist}}

==Bibliography==
*{{cite book |last1=Yoshida |first1 = Zenko|first2 = Stephen G.|last2 = Johnson|first3 = Takaumi|last3 = Kimura|first4 = John R.|last4=Krsul|ref=Yoshida et al.|contribution = Neptunium|title = The Chemistry of the Actinide and Transactinide Elements|editor1-first = Lester R.|editor1-last = Morss|editor2-first = Norman M.|editor2-last = Edelstein|editor3-first = Jean|editor3-last = Fuger|edition = 3rd|date = 2006|volume = 3|publisher = Springer|location = Dordrecht, the Netherlands|pages = 699–812|url = http://radchem.nevada.edu/classes/rdch710/files/neptunium.pdf|doi = 10.1007/1-4020-3598-5_6}}


{{Neptunium compounds}} {{Neptunium compounds}}
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] ]
] ]
]

Latest revision as of 09:07, 29 June 2024

Neptunocene
Names
IUPAC name Bis(η-cyclooctatetraenyl)neptunium(IV)
Other names Neptunium cyclooctatetraenide
Np(COT)2
Identifiers
CAS Number
3D model (JSmol)
InChI
  • InChI=1S/2C5H5.Np/c2*1-2-4-5-3-1;/h2*1-5H;/q2*-1;+2Key: FXDJOXAJBKYPFW-UHFFFAOYSA-N
SMILES
  • c1=cc=cc=c1..c1=cc=cc=c1
Properties
Chemical formula C16H16Np
Molar mass 445 g·mol
Appearance dark brown crystals as a solid, yellow in dilute solution
Solubility in water insoluble, does not react with water
Solubility in chlorocarbons sparingly soluble (ca. 0.5 g/L)
Hazards
Occupational safety and health (OHS/OSH):
Main hazards radiation hazard, pyrophoric
Except where otherwise noted, data are given for materials in their standard state (at 25 °C , 100 kPa). Infobox references
Chemical compound

Neptunocene, Np(C8H8)2, is an organoneptunium compound composed of a neptunium atom sandwiched between two cyclooctatetraenide (COT) rings. As a solid it has a dark brown/red colour but it appears yellow when dissolved in chlorocarbons, in which it is sparingly soluble. The compound is quite air-sensitive.

It was one of the first organoneptunium compounds to be synthesised, and is a member of the actinocene family of actinide-based metallocenes.

Structure

The sandwich structure of neptunocene has been determined by single crystal XRD. The COT rings are found to be planar with 8 equivalent C–C bonds of 1.385 Å length, and sit parallel in an eclipsed conformation. The Np–COT distance (to the ring centroid) is 1.909 Å and the individual Np–C distances are 2.630 Å.

Neptunocene assumes a monoclinic crystal structure (P21/n space group) which is isomorphous to uranocene and thorocene but not to plutonocene.

Synthesis and properties

Neptunocene was first synthesised in 1970 by reacting neptunium(IV) chloride (NpCl4) with dipotassium cyclooctatetraenide (K2(C8H8)) in diethyl ether or THF:

NpCl4 + 2 K2(C8H8) → Np(C8H8)2 + 4 KCl

The same reaction conditions have been routinely reproduced since then for the synthesis of the compound.

The three actinocenes uranocene, neptunocene, and plutonocene share virtually identical chemistry: they do not react in the presence of water or dilute base, but are very air-sensitive, quickly forming oxides. All three are only slightly soluble (up to about 10 M concentrations) in aromatic or chlorinated solvents such as benzene, toluene, carbon tetrachloride or chloroform.

References

  1. ^ Karraker, David G.; Stone, John Austin.; Jones, Erwin Rudolph.; Edelstein, Norman. (1970). "Bis(cyclooctatetraenyl)neptunium(IV) and bis(cyclooctatetraenyl)plutonium(IV)". Journal of the American Chemical Society. 92 (16): 4841–4845. doi:10.1021/ja00719a014. ISSN 0002-7863. Archived from the original on 2024-05-03. Retrieved 2021-03-22.
  2. ^ Greenwood, Norman N.; Earnshaw, Alan (1997). Chemistry of the Elements (2nd ed.). Butterworth-Heinemann. pp. 1278–1280. ISBN 9780750633659.
  3. ^ Eisenberg, David C.; Streitwieser, Andrew; Kot, Wing K. (1990). "Electron transfer in organouranium and transuranium systems". Inorganic Chemistry. 29 (1): 10–14. doi:10.1021/ic00326a004. ISSN 0020-1669. Archived from the original on 2024-05-03. Retrieved 2021-03-22.
  4. ^ Ridder, D. J. A. De; Rebizant, J.; Apostolidis, C.; Kanellakopulos, B.; Dornberger, E. (1996). "Bis(cyclooctatetraenyl)neptunium(IV)". Acta Crystallographica Section C. 52 (3): 597–600. doi:10.1107/S0108270195013047. ISSN 1600-5759. Archived from the original on 2021-06-12. Retrieved 2021-03-22.
  5. ^ Yoshida, Zenko; Johnson, Stephen G.; Kimura, Takaumi; Krsul, John R. (2006). "Neptunium". In Morss, Lester R.; Edelstein, Norman M.; Fuger, Jean (eds.). The Chemistry of the Actinide and Transactinide Elements (PDF). Vol. 3 (3rd ed.). Dordrecht, the Netherlands: Springer. pp. 699–812. doi:10.1007/1-4020-3598-5_6. Archived from the original (PDF) on 2018-01-17. Retrieved 2016-08-07.
Neptunium compounds
Np(III)
Np(IV)
Organoneptunium(IV) compounds
Np(V)
Np(VI)
Np(VII)
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