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{{Chembox {{Chembox
| Verifiedfields = changed
⚫ | verifiedrevid = 394839932
| Watchedfields = changed
| ImageFile = Osmocene.svg
⚫ | verifiedrevid = 428743038
| ImageSize = 100px
| ImageFile = Osmocene_Eclipsed_Conformer_Structural_Formula.svg
| ImageAlt =
| IUPACName = | ImageSize = 100px
| PIN = | ImageAlt =
| PIN = Osmocene<ref>{{cite book |author=] |date=2014 |title=Nomenclature of Organic Chemistry: IUPAC Recommendations and Preferred Names 2013 |publisher=] |pages=1041 |doi=10.1039/9781849733069 |isbn=978-0-85404-182-4}}</ref>
| OtherNames =
| OtherNames = {{ubl|Di(cyclopentadienyl)osmium|Bis(η<sup>5</sup>-cyclopentadienyl)osmium}}
| Section1 = {{Chembox Identifiers |Section1={{Chembox Identifiers
| CASNo =1273-81-0 | CASNo =1273-81-0
| CASNo_Ref = {{cascite}} | CASNo_Ref = {{cascite|correct|??}}
| PubChem =
| SMILES = }} | PubChem = 6432038
| ChemSpiderID_Ref = {{chemspidercite|changed|chemspider}}
⚫ | Section2 = {{Chembox Properties
| ChemSpiderID = 71493
⚫ | C = 10 | H = 10 | Os = 1
| SMILES = 1cccc1.1cccc1.
⚫ | Appearance =
| InChI = 1/2C5H5.Os/c2*1-2-4-5-3-1;/h2*1-5H;/q2*-1;+2
⚫ | Density =
| InChIKey = RMYKEUKAFJLONI-UHFFFAOYAC
⚫ | MeltingPt =
| StdInChI_Ref = {{stdinchicite|changed|chemspider}}
⚫ | BoilingPt =
| StdInChI = 1S/2C5H5.Os/c2*1-2-4-5-3-1;/h2*1-5H;/q2*-1;+2
⚫ | Solubility = }}

⚫ | Section3 = {{Chembox Hazards
| StdInChIKey_Ref = {{stdinchicite|changed|chemspider}}
⚫ | MainHazards =
| StdInChIKey = RMYKEUKAFJLONI-UHFFFAOYSA-N }}
⚫ | FlashPt =
⚫ |Section2={{Chembox Properties
| Autoignition = }}
⚫ | C=10 | H=10 | Os=1
⚫ | Appearance = white solid
⚫ | Density =
⚫ | MeltingPt = 234 °C
⚫ | BoilingPt = 298 °C
⚫ | Solubility =
}}
|Section3={{Chembox Structure
| Structure_ref = <ref name="structure"/>
| CrystalStruct = orthorhombic
| PointGroup = D<sub>5h</sub>
| SpaceGroup = Pnma, No. 62
}}
⚫ |Section4={{Chembox Hazards
⚫ | MainHazards =
⚫ | FlashPt =
| AutoignitionPt =
}}
|Section5={{Chembox Related
| OtherCompounds = ], ]
}}
}} }}


'''Osmocene''' is an ] found as a white solid. It is a ]. '''Osmocene''' is an ] found as a white solid. It is a ] with the formula Os(C<sub>5</sub>H<sub>5</sub>)<sub>2</sub>.


== Synthesis ==
Osmocene is commercially available. It may be prepared by the reaction of ] with ], followed by ] and ].<ref>{{cite journal | last1 = Bobyens | first1 = J. C. A. | last2 = Levendis | first2 = D. C. | last3 = Bruce | first3 = Michael I. | last4 = Williams | first4 = Michael L. | title = Crystal structure of osmocene, Os(&eta;-C<sub>5</sub>H<sub>5</sub>)<sub>2</sub> | journal = Journal of Crystallographic and Spectroscopic Research | volume = 16 | pages = 519 | year = 1986 | doi = 10.1007/BF01161040}}</ref> Osmocene is commercially available. It may be prepared by the reaction of ] with ] followed by ] and ].<ref name="structure">{{cite journal | last1 = Bobyens | first1 = J. C. A. | last2 = Levendis | first2 = D. C. | last3 = Bruce | first3 = Michael I. | last4 = Williams | first4 = Michael L. | title = Crystal structure of osmocene, Os(η-C<sub>5</sub>H<sub>5</sub>)<sub>2</sub> | journal = Journal of Crystallographic and Spectroscopic Research | volume = 16 | pages = 519 | year = 1986 | doi = 10.1007/BF01161040 | issue = 4| s2cid = 96874978 }}</ref>

It was first synthesized by ] and Heinrich Grumbert via the reaction of ] with excess ] in ], where osmium(II) chloride is presumed to be an intermediate formed ''in situ''. Alternatively, ] could be reacted with osmium(IV) chloride, though this has worse yields.<ref>{{cite journal|last1=Fischer|first1=Ernst Otto|last2=Grumbert|first2=Heinrich|title=Über Aromatenkomplexe von Metallen, XXIX. Di-cyclopentadienyl-osmium|journal=]|volume=92|issue=9|date=1959|pages=2302–2309|doi=10.1002/cber.19590920948}}</ref>

== Properties ==
Osmocene is a white solid. The molecular structure features an osmium ion sandwiched between two ] rings. It is isomorphous to the lighter homologue ], both crystallizing in an eclipsed conformation. This is in contrast to ], which crystallizes with its rings staggered.<ref name="structure"/>

Compared to ferrocene and ruthenocene, osmocene is less reactive towards electrophilic aromatic substitution but has the greatest tendency towards ] formation with ]s.<ref>{{cite journal|last1=Kur|first1=Sally A.|last2=Rheingold|first2=Arnold L.|last3=Winter|first3=Charles H.|title=Synthesis, Characterization, and Halogenation of Decakis( acetoxymercurio)osmoene. Crystal and Molecular Structure of Decachloroosmocene|journal=]|date=1995 |volume=34|issue=1|pages=414–416|doi=10.1021/ic00105a067}}</ref>

The osmocenium cation <sup>+</sup> dimerizes, forming a binuclear complex with an Os-Os bond.<ref>{{cite journal|last1=Droege|first1=Michael W.|last2=Harman|first2=W. Dean|last3=Taube|first3=Henry|authorlink3=Henry Taube|title=Higher Oxidation State Chemistry of Osmocene: Dimeric Nature of the Osmocenium Ion|journal=]|date=1987 |volume=26|issue=8|pages=1309–1315|doi=10.1021/ic00255a023}}</ref> In contrast, the decamethylosmocenium cation <sup>+</sup> is stable as the monomer.<ref>{{cite book|last=Astruc|first=Didier|authorlink = Didier Astruc|title=Organometallic Chemistry and Catalysis|chapter=Metallocenes and Sandwich Complexes|page=263|publisher=Springer-Verlag|date=2007|isbn=978-3-540-46128-9|doi=10.1007/978-3-540-46129-6_13}}</ref>

==Uses==
In 2009, Horst Kunkely and Arnd Vogler reported the possibility of ] with osmocene as a catalyst.<ref>{{cite journal|last1=Kunkely|first1=Horst|last2=Vogler|first2=Arnd|title=Water Splitting by Light with Osmocene as Photocatalyst|journal=]|volume=48|issue=9|pages=1685–1687|date=2009|doi=10.1002/anie.200804712|pmid=19173275 |doi-access=free}}</ref>


==References== ==References==
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{{Osmium compounds}} {{Osmium compounds}}
{{Cyclopentadienide complexes}}

] ]
] ]

Latest revision as of 09:35, 7 December 2023

Osmocene
Names
Preferred IUPAC name Osmocene
Other names
  • Di(cyclopentadienyl)osmium
  • Bis(η-cyclopentadienyl)osmium
Identifiers
CAS Number
3D model (JSmol)
ChemSpider
ECHA InfoCard 100.013.687 Edit this at Wikidata
PubChem CID
CompTox Dashboard (EPA)
InChI
  • InChI=1S/2C5H5.Os/c2*1-2-4-5-3-1;/h2*1-5H;/q2*-1;+2Key: RMYKEUKAFJLONI-UHFFFAOYSA-N
  • InChI=1/2C5H5.Os/c2*1-2-4-5-3-1;/h2*1-5H;/q2*-1;+2Key: RMYKEUKAFJLONI-UHFFFAOYAC
SMILES
  • 1cccc1.1cccc1.
Properties
Chemical formula C10H10Os
Molar mass 320.42 g·mol
Appearance white solid
Melting point 234 °C
Boiling point 298 °C
Structure
Crystal structure orthorhombic
Space group Pnma, No. 62
Point group D5h
Related compounds
Related compounds ferrocene, ruthenocene
Except where otherwise noted, data are given for materials in their standard state (at 25 °C , 100 kPa). ☒N verify (what is  ?) Infobox references
Chemical compound

Osmocene is an organoosmium compound found as a white solid. It is a metallocene with the formula Os(C5H5)2.

Synthesis

Osmocene is commercially available. It may be prepared by the reaction of osmium tetroxide with hydrobromic acid followed by zinc and cyclopentadiene.

It was first synthesized by Ernst Otto Fischer and Heinrich Grumbert via the reaction of osmium(IV) chloride with excess sodium cyclopentadienide in dimethoxyethane, where osmium(II) chloride is presumed to be an intermediate formed in situ. Alternatively, cyclopentadienyl magnesium bromide could be reacted with osmium(IV) chloride, though this has worse yields.

Properties

Osmocene is a white solid. The molecular structure features an osmium ion sandwiched between two cyclopentadienyl rings. It is isomorphous to the lighter homologue ruthenocene, both crystallizing in an eclipsed conformation. This is in contrast to ferrocene, which crystallizes with its rings staggered.

Compared to ferrocene and ruthenocene, osmocene is less reactive towards electrophilic aromatic substitution but has the greatest tendency towards adduct formation with Lewis acids.

The osmocenium cation dimerizes, forming a binuclear complex with an Os-Os bond. In contrast, the decamethylosmocenium cation is stable as the monomer.

Uses

In 2009, Horst Kunkely and Arnd Vogler reported the possibility of photocatalytic water splitting with osmocene as a catalyst.

References

  1. International Union of Pure and Applied Chemistry (2014). Nomenclature of Organic Chemistry: IUPAC Recommendations and Preferred Names 2013. The Royal Society of Chemistry. p. 1041. doi:10.1039/9781849733069. ISBN 978-0-85404-182-4.
  2. ^ Bobyens, J. C. A.; Levendis, D. C.; Bruce, Michael I.; Williams, Michael L. (1986). "Crystal structure of osmocene, Os(η-C5H5)2". Journal of Crystallographic and Spectroscopic Research. 16 (4): 519. doi:10.1007/BF01161040. S2CID 96874978.
  3. Fischer, Ernst Otto; Grumbert, Heinrich (1959). "Über Aromatenkomplexe von Metallen, XXIX. Di-cyclopentadienyl-osmium". Chem. Ber. 92 (9): 2302–2309. doi:10.1002/cber.19590920948.
  4. Kur, Sally A.; Rheingold, Arnold L.; Winter, Charles H. (1995). "Synthesis, Characterization, and Halogenation of Decakis( acetoxymercurio)osmoene. Crystal and Molecular Structure of Decachloroosmocene". Inorg. Chem. 34 (1): 414–416. doi:10.1021/ic00105a067.
  5. Droege, Michael W.; Harman, W. Dean; Taube, Henry (1987). "Higher Oxidation State Chemistry of Osmocene: Dimeric Nature of the Osmocenium Ion". Inorg. Chem. 26 (8): 1309–1315. doi:10.1021/ic00255a023.
  6. Astruc, Didier (2007). "Metallocenes and Sandwich Complexes". Organometallic Chemistry and Catalysis. Springer-Verlag. p. 263. doi:10.1007/978-3-540-46129-6_13. ISBN 978-3-540-46128-9.
  7. Kunkely, Horst; Vogler, Arnd (2009). "Water Splitting by Light with Osmocene as Photocatalyst". Angew. Chem. Int. Ed. 48 (9): 1685–1687. doi:10.1002/anie.200804712. PMID 19173275.
Osmium compounds
Os(0)
Os(0,I)
Os(I)
Os(I,II)
Os(II)
Organoosmium(II) compounds
  • Os(C5H5)2
    • Os(III)
    Os(IV)
    Os(V)
    Os(VI)
    Os(VII)
    Os(VIII)
    Salts and covalent derivatives of the cyclopentadienide ion
    CpH He
    LiCp Be B CpMe N C5H4O F Ne
    NaCp MgCp2

    MgCpBr

    		Al Si P S Cl Ar
    K CaCp2 ScCp3 TiCp2Cl2

    (TiCp2Cl)2
    TiCpCl3
    TiCp2S5
    TiCp2(CO)2
    TiCp2Me2

    		VCp2

    VCpCh
    VCp2Cl2
    VCp(CO)4

    		CrCp2

    (CrCp(CO)3)2

    		MnCp2 FeCp2

    Fe(η-C5H4Li)2
    ((C5H5)Fe(C5H4))2
    (C5H4-C5H4)2Fe2
    FeCp2PF6
    FeCp(CO)2I

    		CoCp2

    CoCp(CO)2

    		NiCp2

    NiCpNO

    		Cu Zn Ga Ge As Se Br Kr
    Rb Sr Y(C5H5)3 ZrCp2Cl2

    ZrCp2ClH

    		NbCp2Cl2 MoCp2H2

    MoCp2Cl2
    (MoCp(CO)3)2

    		Tc RuCp2

    RuCp(PPh3)2Cl
    RuCp(MeCN)3PF6

    		RhCp2 PdCp(C3H5) Ag Cd InCp SnCp2 Sb Te I Xe
    Cs Ba * LuCp3 HfCp2Cl2 Ta (WCp(CO)3)2 ReCp2H OsCp2 IrCp2 Pt Au Hg TlCp PbCp2 Bi Po At Rn
    Fr Ra ** Lr Rf Db Sg Bh HsCp2 Mt Ds Rg Cn Nh Fl Mc Lv Ts Og
     
    * LaCp3 CeCp3 PrCp3 NdCp3 PmCp3 SmCp3 Eu Gd Tb DyCp3 Ho ErCp3 TmCp3 YbCp3
    ** Ac ThCp3
    ThCp4         		Pa UCp4 Np Pu Am Cm Bk Cf Es Fm Md No
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