Bis(cyclooctatetraene)iron explained

Bis(cyclooctatetraene)iron is an organoiron compound with the formula Fe(C8H8)2, abbreviated Fe(COT)2. It is an air-sensitive black solid that is soluble in diethyl ether and aromatic solvents. The compound decomposes in solution after a few days even under inert atmosphere.[1] It has no known practical applications but has been studied as a soluble source of Fe(0).

Preparation

The laboratory synthesis of Fe(COT)2, using Schlenk techniques, involves reduction of ferric acetylacetonate by triethylaluminium in the presence of 1,3,5,7-cyclooctatetraene:[1]

Fe(C5H7O2)3 + 2 C8H8 + 3 Al(C2H5)3 → Fe(C8H8)2 + 3 Al(C2H5)2(C5H7O2) +  C2H4 +  C2H6

Structure

According to analysis by single crystal X-ray crystallography, the two cyclooctatetraene rings bind differently to the Fe center, leading to the description Fe(η4-C8H8)(η6-C8H8). One cyclooctatetraene ring binds to Fe with two adjacent double bonds. This interaction is similar to that in (η4-C8H8)Fe(CO)3. The two planar groups formed by carbon atoms 1,2,7,8 and carbon atoms 3,4,5,6,7 form a dihedral angle of 33°. The second cyclooctatetraene ring binds through three double bonds. The shape and coordination of the lower ring is similar to that in (η6-C8H8)Mo(CO)3. The non-coordinated double bond has a similar bond length as an ordinary double bond.[2]

In solution, Fe(C8H8)2 is a fluxional molecule such that its 1H NMR spectrum consists of a singlet at room-temperature.[2]

References

  1. Book: Gerlach . D. H. . Schunn . R. A. . Bis(1,3,5,7-cyclooctatetraene)iron(0) . . 1974 . 15 . 1–4 . 10.1002/9780470132463.ch1. 9780470131763 .
  2. G. . Allergra. A.. Colmbo . A. . Immirzi . I. W. . Bassi . The Crystal Structure of Bis(cyclooctatetraene)iron . J. Am. Chem. Soc.. 90. 16 . 1968 . 4454–4456 . 10.1021/ja01018a046.