|Molar mass||208.22 g/mol|
|Melting point||284 to 285 °C (543 to 545 °F; 557 to 558 K)|
|Boiling point||sublimes: 160 °C (320 °F; 433 K) in vacuo|
|Solubility in other solvents||slightly: benzene, THF|
|Dipole moment||0 D|
|Flash point||82 °C; 180 °F; 355 K|
Except where noted otherwise, data is given for materials in their standard state (at 25 °C (77 °F), 100 kPa)
|what is: / ?)(|
Bis(benzene)chromium is the organometallic compound with the formula Cr(η6-C6H6)2. It is sometimes called dibenzenechromium. The compound played an important role in the development of sandwich compounds in organometallic chemistry and is the prototypical complex containing two arene ligands.
The substance is air sensitive and its synthesis requires air-free techniques. It was first prepared by Hafner and Fischer by the reaction of CrCl3, aluminium, and benzene, in the presence of AlCl3. This so-called reductive Friedel-Crafts method was pioneered by E.O. Fischer and his students. The product of the reaction was yellow [Cr(C6H6)2]+, which was then reduced to the neutral complex. Idealized equations for the synthesis are:
- CrCl3 + 2/3 Al + AlCl3 + 2 C6H6 → [Cr(C6H6)2]AlCl4 + 2/3 AlCl3
- [Cr(C6H6)2]AlCl4 + 1/2 Na2S2O4 → [Cr(C6H6)2] + NaAlCl4 + SO2
Compounds closely related to [Cr(C6H6)2]+ had been prepared many years before Fischer's work by Franz Hein by the reaction of phenylmagnesium bromide and CrCl3. Hein's reaction affords cationic sandwich complexes containing bi- and terphenyl, which baffled chemists until the breakthrough by Fischer and Hafner. (Indeed, although Harold Zeiss and Minoru Tsutsui of Yale University had earlier proposed the "sandwich" structure, they were unable to convince skeptical journal referees to publish their manuscript until Fischer and Hafner's results were made known.) Fischer and Seus soon prepared Hein's [Cr(C6H5-C6H5)2]+ by an unambiguous route, thus confirming that Hein had unknowingly discovered sandwich complexes, a half-century ahead of the work on ferrocene. Illustrating the rapid pace of this research, the same issue of Chem. Ber. also describes the Mo(0) complex.
The compound reacts with carboxylic acids to give chromium(II) carboxylates, such as chromium(II) acetate, which have interesting structures. Oxidation affords [Cr(C6H6)2]+. Carbonylation gives (benzene)chromium tricarbonyl.
- King, R. B. Organometallic Syntheses. Volume 1 Transition-Metal Compounds; Academic Press: New York, 1965. ISBN 0-444-42607-8
- Elschenbroich, C.; Salzer, A. "Organometallics : A Concise Introduction" (2nd Ed) (1992) Wiley-VCH: Weinheim. ISBN 3-527-28165-7
- Seyferth, D. (2002). "Bis(benzene)chromium. 1. Franz Hein at the University of Leipzig and Harold Zeiss and Minoru Tsutsui at Yale". Organometallics 21 (8): 1520–1530. doi:10.1021/om0201056.
- Seyferth, D. (2002). "Bis(benzene)chromium. 2. Its Discovery by E. O. Fischer and W. Hafner and Subsequent Work by the Research Groups of E. O. Fischer, H. H. Zeiss, F. Hein, C. Elschenbroich, and Others". Organometallics 21 (14): 2800–2820. doi:10.1021/om020362a.
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- Hein, F. (1956). "Zur Frage der Struktur der Chrom-phenyl-Verbindungen. Bemerkungen zur Abhandlung von E. O. Fischer und D. Seus". Chemische Berichte 89 (8): 1816–1821. doi:10.1002/cber.19560890804.
- Fischer, E. O.; Stahl, H.-O. (1956). "Di-benzol-molybdän (O). Über Aromatenkomplexe von Metallen V". Chemische Berichte 89 (8): 1805–1808. doi:10.1002/cber.19560890802.
- Herndon, J. W. "Dibenzenechromium" in Encyclopedia of Reagents for Organic Synthesis (Ed: L. Paquette) 2004, J. Wiley & Sons, New York. doi:10.1002/047084289.