Diiron nonacarbonyl

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Diiron nonacarbonyl
Diiron nonacarbonyl
Diiron nonacarbonyl
Diiron nonacarbonyl
Diiron nonacarbonyl
Sample of diiron nonacarbonyl
Names
IUPAC name
Diiron nonacarbonyl, tri-μ-carbonyl-bis(tricarbonyliron)(Fe—Fe)
Other names
Iron enneacarbonyl
Identifiers
3D model (
JSmol
)
ChemSpider
ECHA InfoCard
 100.035.765 Edit this at Wikidata
EC Number
  • 239-359-5
  • InChI=1S/9CO.2Fe/c9*1-2;; checkY
    Key: JCXLZXJCZPKTBW-UHFFFAOYSA-N checkY
  • InChI=1/9CO.2Fe/c9*1-2;;
    Key: JCXLZXJCZPKTBW-UHFFFAOYAN
  • O=C1[Fe]2(=C=O)(=C=O)(=C=O)C(=O)[Fe]1(=C=O)(=C=O)(=C=O)C2=O
Properties
Fe2C9O9
Molar mass 363.78 g/mol
Appearance orange crystals
Density 2.08 g/cm3
Melting point decomposes at 100 °C[1]
insoluble, does not react with water[2]
Structure
0 D
Hazards
Occupational safety and health (OHS/OSH):
Main hazards
 Toxic, flammable
GHS labelling:
GHS02: FlammableGHS09: Environmental hazardGHS06: Toxic
Danger
Related compounds
Related iron carbonyls
 Iron pentacarbonyl
Triiron dodecacarbonyl
Related compounds
 Dimanganese decacarbonyl
Dicobalt octacarbonyl
Except where otherwise noted, data are given for materials in their standard state (at 25 °C [77 °F], 100 kPa).
checkY verify (what is checkY☒N ?)

Diiron nonacarbonyl is an

organometallic compound with the formula Fe2(CO)9. This metal carbonyl is an important reagent in organometallic chemistry and of occasional use in organic synthesis.[3] It is a more reactive source of Fe(0) than Fe(CO)5. This micaceous orange solid is virtually insoluble in all common solvents
.

Synthesis and structure

Following the original method,[4] photolysis of an acetic acid solution of Fe(CO)5 produces Fe2(CO)9 in good yield:[5][6]

2 Fe(CO)5 → Fe2(CO)9 + CO

Fe2(CO)9 consists of a pair of Fe(CO)3 centers linked by three bridging CO ligands. Although older textbooks show an Fe-Fe bond consistent with the

banana bond" for one of the bridging carbonyls. The minor isomer has been crystallized together with C60. The iron atoms are equivalent and octahedral molecular geometry. Elucidation of the structure of Fe2(CO)9 proved to be challenging because its low solubility inhibits growth of crystals. The Mößbauer spectrum
reveals one quadrupole doublet, consistent with the D3h-symmetric structure.

Reactions

Fe2(CO)9 is a precursor to compounds of the type Fe(CO)4L and Fe(CO)3(diene). Such syntheses are typically conducted in

THF solution. In these conversions, it is proposed that small amounts of Fe2(CO)9 dissolve according to the following reaction:[8]

Fe2(CO)9 → Fe(CO)5 + Fe(CO)4(THF)

Oxidative addition of allyl bromide to diiron nonacarbonyl gives the

allyl iron(II) derivaive:[9]

Fe2(CO)9 + BrCH2CH=CH2 → FeBr(CO)3(C3H5) + CO + Fe(CO)5

Cyclobutadieneiron tricarbonyl is prepared similarly using 3,4-dichlorocyclobutene:[10]

C4H4Cl2 + 2 Fe2(CO)9 → (C4H4)Fe(CO)3 + 2 Fe(CO)5 + 2 CO + 2 FeCl2.

Fe2(CO)9 has also been employed in the synthesis of cyclopentadienones via a net [2+3]-cycloaddition from dibromoketones, known as the Noyori [3+2] reaction.[11]

Low temperature UV/vis photolysis of Fe2(CO)9 yields the Fe2(CO)8 unsaturated complex, producing both CO-bridged and unbridged isomers.[12]

Safety

Metal carbonyls are typically treated as if they are highly toxic.[5]

References

  1. ^ Dewar, J., & Jones, H. O. (1907). On a New Iron Carbonyl, and on the Action of Light and of Heat on the Iron Carbonyls. Proceedings of the Royal Society A: Mathematical, Physical and Engineering Sciences, 79(527), 66–80. doi:10.1098/rspa.1907.0015
  2. ^ Diiron nonacarbonyl, reactivity
  3. ISBN 3-527-28165-7
  4. doi:10.1002/cber.19270600626
    .
  5. ^
    ISBN 0-444-42607-8
    .
  6. ISBN 978-0-470-13239-5. {{cite book}}: |journal= ignored (help
    )
  7. doi:10.1039/c2cc35304k
  8. doi:10.1021/ja00818a016
  9. doi:10.1021/ja00481a020
    .
  10. doi:10.15227/orgsyn.050.0021
    .
  11. R. Noyori; Yokoyama, K.; Hayakawa, Y. (1988). "Cyclopentanones from α, α'-Dibromoketones and Enamines: 2,5-Dimethyl-3-Phenyl-2-Cyclopenten-1-one". Organic Syntheses
    ; Collected Volumes, vol. 6, p. 520.
  12. doi:10.1021/ic00240a014
    .
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