In the late 1910s, Franz Hein started the investigation of "triphenylchromium" by reacting chromium trichloride with a Grignard reagent, phenyl magnesium bromide. Such a reaction gave a mixture of phenyl chromium and Hein suggested that it contained a Cr(VI) species, "(C6H5)5CrBr", generated via valence disproportionation.[1][2]
This event marked an advance in organochromium chemistry at the time and "(C6H5)5CrBr" was described to have salt-like properties. However, the reported workup procedures for "(C6H5)5CrBr" was challenging and the yield was low.[1][2] Later scrutinization by Zeiss and Tsutsui revealed that Hein's formulation of the chromium-containing products was flawed.[1]
Preparation
The actual discovery of bis(benzene)chromium was largely contributed by Ernst Otto Fischer and Walter Hafner in the 1950s. Ernst Otto Fischer postulated that it might be possible to synthesize a neutral chromium(0) complex with two benzene ligands, which has a sandwich structure, similar to that of ferrocene. In 1954, Walter Hafner, a PhD student of Ernst Otto Fischer at the time, put the idea into practice. A reaction of chromium trichloride, aluminium trichloride, aluminium powder in m-xylene resulted in the formation of yellow [Cr(C6H6)2]+, which was then reduced by sodium dithionite in aqueous sodium hydroxide. The resulting solid was determined to be the target, bis(benzene)chromium.[3][4]
6 C6H6 + 3 CrCl3 + 2 Al + x AlCl3 → 3 [(C6H6)2Cr][AlCl4]·(x−1)AlCl3
It was noted that excess aluminium trichloride is needed to solubilize the product.[3] The substance is air sensitive and its synthesis requires air-free techniques. The reaction, utilizing Al and AlCl3, is so-called the reductive Friedel-Crafts method pioneered by Fischer and his students.[5][6]
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.[7][8] Illustrating the rapid pace of this research, the same issue of Chem. Ber. also describes the Mo(0) complex.[9]
Using the technique of metal vapor synthesis, bis(benzene)chromium and many analogous compounds can be prepared by co-condensation of Cr vapor and arenes. In this way, the phosphabenzene complex [Cr(C5H5P)2] can be prepared.[10]
Properties and characterization
Bis(benzene)chromium is thermally stable under an inert gas atmosphere. As predicted, it is diamagnetic with a dipole moment of zero. In 1956, Fischer and Weiss reported the crystal structure of bis(benzene)chromium to be centrosymmetric and has a cubic symmetry.[11] Electrochemical studies of bis(benzene)chromium suggested that the half-wave potential (E1/2) of the +1/0 couple is around -1.10 to -1.25 V versus Fc+/Fc at 298.15K, depending on the experimental conditions.[12][13][14]
Bonding and electronic structure
Theoretical chemical bonding of bis(benzene)chromium have been investigated since the discovery of this compound. The ground state configuration is (3e2g)4(4a1g)2 (3e2u)0. Analysis of the frontier orbitals suggested that the chromium-benzene interaction is largely contributed by the 𝝅 and/or 𝞭 interactions between the 3d metal orbitals and ligand 𝝅 orbitals.[15][16] 3e2g (HOMO-1) and 3e1g (HOMO-2) molecular orbitals are 𝞭-bonding interactions between metal 3d𝞭 and ligand 𝝅 orbitals. The highest occupied molecular orbital (HOMO), 4a1g, is the non-bonding metal dz2 orbital. The lowest unoccupied molecular orbital (LUMO) is 3e2u, which is purely ligand 𝝅 orbital. As for 4e1g (LUMO+1) and 4e2g (LUMO+2), they are composed of anti-bonding interaction between 3d𝝅 and ligand 𝝅 orbitals.
Molecular orbitals of bis(benzene)chromium, visualized by IboView. (Top to bottom: LUMO+2, LUMO+1, LUMO, HOMO, HOMO-1, HOMO-2)
Charge Distribution (%) of Ground State Bis(benzene)chromium[16]
Cr
C
H
Molecular Orbital
No. of Electrons
s
p
d
s
p𝝈
p𝝅
s
4e1g
0
73
2
2
10
3e2u
0
73
4a1g
2
1
82
1
1
1
3e2g
4
50
2
21
3e1g
4
16
1
52
4e1u
4
4
49
2e2u
4
60
17
2e2g
4
1
60
18
4a2u
2
4
61
3a1g
2
8
53
3d orbitals population of chromium(0) in bis(benzene)chromium was investigated, utilizing NBO analysis. While e2g largely results from electron donation from the metal to the ligand, e1g is mainly composed of the electrons donated from the benzene ligands.[17]
3d orbital population of Cr in Bis(benzene)chromium[17]
Molecular Orbitals
NBO
X-ray
4a1g
1.896/36%
1.62(1)/35%
3e2g
2.412/45%
1.953(7)/42%
3e1g
1.026/19%
1.112(7)/24%
In contrast to ferrocene, where 𝝅-interactions dominate the metal-ligand bonds, 𝞭-interactions play a significant role in bis(benzene)chromium.[15][16]
Energy Decomposition Analysis at BP86/TZP of Ferrocene and Bisbenzenechromium[15]
In late 1990s, Samuel and coworkers revealed that bis(benzene)chromium is an efficient organometallic radical scavenger. In contrast to cobaltocene, which traps radicals (R．) to form 19-valence electron species (η5-C5H5)(η4-C5H5R)Co, bis(benzene)chromium reacts with radicals to form 17-valence electron species (η6-C6H6)(η5-C6H6R)Cr (R = H, D, isobutyronitrile).[18]
Spin trapping by bis(benzene)chromium (R = H, D, isobutyronitrile)[18]
Subsequently, Bis(benzene)chromium was reported to catalyze hydrosilation of alcohols and aldehydes. Unlike late transition metal catalyzed processes involving oxidative addition, the mechanism of this reaction might involve radicals and hydrogen atom abstraction.[19]
Hydrosilation of ketones catalyzed by bis(benzene)chromium[19]
^King, R. B. Organometallic Syntheses. Volume 1 Transition-Metal Compounds; Academic Press: New York, 1965. ISBN0-444-42607-8
^Elschenbroich, C.; Salzer, A. "Organometallics : A Concise Introduction" (2nd Ed) (1992) Wiley-VCH: Weinheim. ISBN3-527-28165-7
^Fischer, E. O; Seus, D. (1956). "Zur Frage der Struktur der Chrom-phenyl-Verbindungen. Über Aromatenkomplexe von Metallen VI". Chemische Berichte. 89 (8): 1809–1815. doi:10.1002/cber.19560890803.
^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.
^E. Schmidt, K. J. Klabunde, A. Ponce, A. Smetana, D. Heroux "Metal Vapor Synthesis of Transition Metal Compounds" Encyclopedia of Inorganic Chemistry 2006, John Wiley & Sons. doi:10.1002/0470862106.ia137
^Herndon, J. W. "Dibenzenechromium" in Encyclopedia of Reagents for Organic Synthesis (Ed: L. Paquette) 2004, J. Wiley & Sons, New York. doi:10.1002/047084289X.
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