(Benzene)chromium tricarbonyl

(Benzene)chromium(0) tricarbonyl

Names
IUPAC name (benzene)tricarbonylchromium
Other names benzene tricarbonyl chromium, (benzene)chromium tricarbonyl, Benchrotrene, pi-benzenetricarbonylchromium
Identifiers
CAS Number	12082-08-5  N
3D model (JSmol)	Interactive image
ChemSpider	9130108  Y
ECHA InfoCard	100.031.939
EC Number	235-146-6
PubChem CID	10954891
InChI InChI=1S/C6H6.3CO.Cr/c1-2-4-6-5-3-1;3*1-2;/h1-6H;;;; Y Key: WVSBQYMJNMJHIM-UHFFFAOYSA-N Y InChI=1/C6H6.3CO.Cr/c1-2-4-6-5-3-1;3*1-2;/h1-6H;;;; Key: WVSBQYMJNMJHIM-UHFFFAOYAR
SMILES [Cr].[O+]#[C-].[O+]#[C-].[O+]#[C-].c1ccccc1
Properties
Chemical formula	Cr(C6H6)(CO)3
Molar mass	214.14 g/mol
Appearance	solid yellow crystals
Melting point	163 to 166 °C (325 to 331 °F; 436 to 439 K)
Solubility in water	nonsoluble
Solubility	THF, ether, benzene
Structure
Coordination geometry	tetrahedral, "piano stool"
Hazards
Occupational safety and health (OHS/OSH):
Main hazards	Harmful through inhalation, contact with skin, or swallowed
GHS labelling:
Pictograms
Signal word	Warning
Hazard statements	H302, H312, H332
Precautionary statements	P261, P264, P270, P271, P280, P301+P312, P302+P352, P304+P312, P304+P340, P312, P322, P330, P363, P501
Except where otherwise noted, data are given for materials in their standard state (at 25 °C [77 °F], 100 kPa). N  verify  (what is  YN ?) Infobox references

(Benzene)chromium tricarbonyl is an organometallic compound with the formula Cr(C₆H₆)(CO)₃. 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)₆) and traces of Cr(C₆H₆)(CO)₃. The synthesis was optimized through the reaction of Cr(CO)₆ and Cr(C₆H₆)₂. For commercial purposes, a reaction of Cr(CO)₆ and benzene is used:

Cr(CO)₆ + C₆H₆ → Cr(C₆H₆)(CO)₃ + 3 CO

Reactions

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.

(Arene)Cr(CO)₃ compounds undergo ligand exchange both thermally and photochemically: the arene is thermally labile, whereas the carbonyls are photolytically so. ^[5]

References

1. Gilbert T. M. Bauer C. B., Rogers R. D. (1996). "Structures of (η⁶-benzene dimethylacetal)- and (η⁶-benzene diethylacetal)chromium tricarbonyl: structural evidence for the near-electroneutrality of the dialkylacetal substituent". Journal of Chemical Crystallography . 26 (5): 355. doi:10.1007/BF01677100. S2CID   91957129.
2. Fischer, Ernst Otto; Őfele, Karl. (1957). "Über Aromatenkomplexe von Metallen, XIII Benzol-Chrom-Tricarbonyl," Chemische Berichte, 90, 2532-5. doi : 10.1002/cber.19570901117.
3. E. Peter Kündig (2004). "Synthesis of Transition Metal η⁶-Arene Complexes". Topics Organomet Chem. Topics in Organometallic Chemistry. 7: 3–20. doi:10.1007/b94489. ISBN   978-3-540-01604-5.
4. Herndon, James W; Laurent, Stéphane E. (2008). "(η⁶-Benzene)tricarbonylchromium," in Encyclopedia of Reagents for Organic Synthesis, John Wiley & Sons, Chichester, 2008. doi : 10.1002/047084289X.rb025.pub2. Article Online Posting Date: March 15, 2009
5. Heenan, Davnat (Sep 2002). The Photochemistry of Azaferrocene and its Derivatives (PDF) (PhD thesis). Dublin City University. p. 68.