(Benzene)chromium tricarbonyl explained

(Benzene)chromium tricarbonyl is an organometallic compound with the formula . This yellow crystalline solid compound is soluble in common nonpolar organic solvents. The molecule adopts a geometry known as “piano stool” because of the planar arrangement of the aryl group and the presence of three CO ligands as "legs" on the chromium-bond axis.[1]

Preparation

(Benzene)tricarbonylchromium was first reported in 1957 by Fischer and Öfele, who prepared the compound by the carbonylation of bis(benzene)chromium.[2] They obtained mainly chromium carbonyl (Cr(CO)) and traces of Cr(CH)(CO). The synthesis was optimized through the reaction of Cr(CO) and Cr(CH). For commercial purposes, a reaction of Cr(CO) and benzene is used:

Cr(CO) + CH → Cr(CH)(CO) + 3 CO

Applications

Complexes of the type (Arene)Cr(CO)3 have been well investigated as reagents in organic synthesis..[3] The aromatic ring of (benzene)tricarbonylchromium is substantially more electrophilic than benzene itself, allowing it to undergo nucleophilic addition reactions.[4]

It is also more acidic, undergoing lithiation upon treatment with n-butyllithium. The resulting organolithium compound can then be used as a nucleophile in various reactions, for example, with trimethylsilyl chloride:

(Benzene)tricarbonylchromium is a useful catalyst for the hydrogenation of 1,3-dienes. The product alkene results from 1,4-addition of hydrogen. The complex does not hydrogenate isolated double bonds.

References

  1. Gilbert T. M. Bauer C. B., Rogers R. D. . Structures of (η-benzene dimethylacetal)- and (η-benzene diethylacetal)chromium tricarbonyl: structural evidence for the near-electroneutrality of the dialkylacetal substituent . . 10.1007/BF01677100 . 1996 . 26 . 355 . 5. 91957129 .
  2. Fischer, Ernst Otto; Őfele, Karl. (1957). “Über Aromatenkomplexe von Metallen, XIII Benzol-Chrom-Tricarbonyl,” Chemische Berichte, 90, 2532-5. .
  3. Topics Organomet Chem.. 2004. 7. 3–20. 10.1007/b94489. Synthesis of Transition Metal η6-Arene Complexes. E. Peter Kündig. Topics in Organometallic Chemistry. 978-3-540-01604-5.
  4. Herndon, James W; Laurent, Stéphane E. (2008). “(η-Benzene)tricarbonylchromium,” in Encyclopedia of Reagents for Organic Synthesis, John Wiley & Sons, Chichester, 2008. . Article Online Posting Date: March 15, 2009