Misplaced Pages

Cobaltocene: Difference between revisions

Article snapshot taken from Wikipedia with creative commons attribution-sharealike license. Give it a read and then ask your questions in the chat. We can research this topic together.
Browse history interactively← Previous editNext edit →Content deleted Content addedVisualWikitext
Revision as of 10:01, 21 October 2011 editCitation bot 1 (talk | contribs)Bots130,044 editsm Add: issue.← Previous edit Revision as of 11:15, 21 October 2011 edit undoBeetstra (talk | contribs)Edit filter managers, Administrators172,031 edits Script assisted update of identifiers for the Chem/Drugbox validation project (updated: 'ChEBI').Next edit →
Line 22: Line 22:
| CASNo = 1277-43-6 | CASNo = 1277-43-6
| ChEBI_Ref = {{ebicite|correct|EBI}} | ChEBI_Ref = {{ebicite|correct|EBI}}
| ChEBI = 30678 | ChEBI = <!-- blanked - oldvalue: 30678 -->
| EINECS = | EINECS =
| RTECS = GG0350000 | RTECS = GG0350000

Revision as of 11:15, 21 October 2011

Cobaltocene
Skeletal formula of cobaltocene
Skeletal formula of cobaltocene
Ball-and-stick model of cobaltocene
Ball-and-stick model of cobaltocene
Names
IUPAC names cobaltocene,
bis(η- cyclopentadienyl)-
cobalt
Other names Cp2Co
Identifiers
CAS Number
3D model (JSmol)
ChemSpider
ECHA InfoCard 100.013.692 Edit this at Wikidata
RTECS number
  • GG0350000
CompTox Dashboard (EPA)
InChI
  • InChI=1S/2C5H5.Co/c2*1-2-4-5-3-1;/h2*1-5H;/q2*-1;+2Key: ILZSSCVGGYJLOG-UHFFFAOYSA-N
  • InChI=1/2C5H5.Co/c2*1-2-4-5-3-1;/h2*1-5H;/q2*-1;+2Key: ILZSSCVGGYJLOG-UHFFFAOYAM
SMILES
  • 1cccc1.1cccc1.
Properties
Chemical formula
Molar mass 189.12 g/mol
Solubility in water not soluble
Structure
Coordination geometry sandwich
Dipole moment zero
Thermochemistry
Std molar
entropy (S298) 		236 J.K.mol
Std enthalpy of
formation (ΔfH298) 		+237 kJ/mol (uncertain)
Std enthalpy of
combustion (ΔcH298) 		-5839 kJ/mol
Hazards
NFPA 704 (fire diamond)
NFPA 704 four-colored diamondHealth 1: Exposure would cause irritation but only minor residual injury. E.g. turpentineFlammability 2: Must be moderately heated or exposed to relatively high ambient temperature before ignition can occur. Flash point between 38 and 93 °C (100 and 200 °F). E.g. diesel fuelInstability 0: Normally stable, even under fire exposure conditions, and is not reactive with water. E.g. liquid nitrogenSpecial hazards (white): no code
1 2 0
Related compounds
Except where otherwise noted, data are given for materials in their standard state (at 25 °C , 100 kPa). checkY verify (what is  ?) Infobox references
Chemical compound

Cobaltocene, known also as bis(cyclopentadienyl)cobalt(II) or even "bis Cp cobalt", is an organocobalt compound with the formula Co(C5H5)2. It is a dark purple solid that sublimes readily slightly above room temperature. Cobaltocene was discovered shortly after ferrocene, the first metallocene. Due to the ease with which it reacts with O2, the compound must be handled and stored using air-free techniques.

Synthesis

Cobaltocene is prepared by the reaction of sodium cyclopentadienide (NaC5H5) with anhydrous cobalt(II) chloride in THF solution. Sodium chloride is cogenerated, and the organometallic product is usually purified by vacuum sublimation.

Structure and bonding

In Co(C5H5)2 the Co centre is "sandwiched" between two cyclopentadienyl (Cp) rings. The Co-C bond lengths are about 2.1 Å, slightly longer than the Fe-C bond in ferrocene.

Co(C5H5)2 belongs to a group of organometallic compounds called metallocenes or sandwich compounds.Cobaltocene has 19 valence electrons, one more than usually found in organotransition metal complexes, such as its very stable relative ferrocene. (See 18-electron rule.) This additional electron occupies an orbital that is antibonding with respect to the Co-C bonds. Consequently, the Co-C distances are slightly longer than the Fe-C bonds in ferrocene. Many chemical reactions of Co(C5H5)2 are characterized by its tendency lose this "extra" electron, yielding 18-electron cation known as cobaltocenium:

2Co(C5H5)2 + I2 → 2 + 2I
19e
    
18e
  

The otherwise close relative of cobaltocene, rhodocene does not exist as a monomer, but spontaneously dimerizes by formation of a C-C bond between Cp rings.

Reactions

Redox properties

Co(C5H5)2 is a common one-electron reducing agent in the laboratory. In fact, the reversibility of the Co(C5H5)2 redox couple is so well behaved that Co(C5H5)2 may be used in cyclic voltammetry as an internal standard. Its permethylated analogue decamethylcobaltocene (Co(C5Me5)2) is an especially powerful reducing agent, due to inductive donation of electron density from the 10 methyl groups, prompting the cobalt to give up its "extra" electron even more so. These two compounds are rare examples of reductants that dissolve in non-polar organic solvents. The reduction potentials of these compounds follow, using the ferrocene-ferrocenium couple as the reference:

Fe(C5H5)2/Fe(C5H5)2: 0 V
Fe(C5Me5)2/Fe(C5Me5)2: -0.59
Co(C5H5)2/Co(C5H5)2: -1.33
Co(C5Me5)2/Co(C5Me5)2: -1.94

The data show that the decamethyl compounds are ca. 600 mV more reducing than the parent metallocenes. This substituent effect is, however, overshadowed by the influence of the metal: changing from Fe to Co renders the reduction more favorable by over 1.3 volts.

Carbonylation

Treatment of Co(C5H5)2 with carbon monoxide gives the cobalt(I) derivative Co(C5H5)(CO)2, concomitant with loss of one Cp ligand.

References

  1. ^ King, R. B. “Organometallic Syntheses” Volume 1: Academic Press: New York, 1965.
  2. M. Yu. Antipin, R. Boese, N. Augart, G. Schmid "Redetermination of the cobaltocene crystal structure at 100 K and 297 K: Comparison with ferrocene and nickelocene" Structural Chemistry 1993, Volume 4, Number 2, 91-101. doi:10.1007/BF00677370
  3. C. Elschenbroich, A. Salzer ”Organometallics : A Concise Introduction” (2nd Ed) (1992) from Wiley-VCH: Weinheim. ISBN 3-527-28165-7
  4. N. G. Connelly, W. E. Geiger (1996). "Chemical Redox Agents for Organometallic Chemistry". Chem. Rev. 96 (2): 877–910. doi:10.1021/cr940053x. PMID 11848774.

External links

Categories: