User:Circador/Cyclobutadieneiron tricarbonyl
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[edit]Lead
[edit]Cyclobutadieneiron tricarbonyl is an organoiron compound with the formula Fe(C4H4)(CO)3. The molecule is a low melting point, yellow solid that is soluble in organic solvents, and sublimes at high vacuum. Initially postulated by Longuet-Higgins and Orgel in 1956, it is notable as the first isolable example of an unsubstituted cyclobutadiene species. Through studies of structure and reactivity, it has helped uncover fundamental information about the ground state of cyclobutadiene, contribute to the theory of metalloaromaticity, and enable new reactions in organic chemistry as a precursor for cyclobutadiene, which is an elusive species in the free state.[1]
Synthesis
[edit]Via cyclobutene derivatives
[edit]It was first prepared in 1965 by Pettit from 3,4-dichlorocyclobutene and diiron nonacarbonyl:[2][3]
- C4H4Cl2 + 2 Fe2(CO)9 → (C4H4)Fe(CO)3 + 2 Fe(CO)5 + 5 CO + FeCl2
Pettit, Amiet, and Reeves further generalized this synthesis by using the sodium salt of iron carbonyl anion Na2Fe(CO)4 to make it, which could be extended to other metals and substituted dihalocyclobutenes.
C4H4Cl2 + NaFe(CO)4 → (C4H4)Fe(CO)3 + CO + 2NaCl
In 1967, it was prepared by reaction of iron pentacarbonyl with photo-α-pyrone via brief irradiation by Rosenblum and Gatsonis.[4]
Although the tetraphenyl-substituted cyclobutadieneiron tricarbonyl was prepared in 1959 by Hubel, in 1973 Buhler was able to cyclodimerize acetylene directly at high temperature and pressure of 110 °C and 9,000 atm in order to make cyclobutadieneiron tricarbonyl among other byproducts.[5]
Fe(CO)5 + 2HCCH → (C4H4)Fe(CO)3 + 2 CO
Substituted cyclobutadieneiron iron tricarbonyl complexes can also be prepared via reacting alkadiynes with iron carbonyls, such as in 1972 by Eavenson.[6]
Tetramethyl and tetraphenyl-substituted cyclobutadiene iron complexes have also been synthesized in low to moderate yields by transferring the substituted cyclobutadiene ligand from Ni, Pd, or Pt cyclobutadiene complexes under reflux.[5]
Structure and Bonding
[edit]Cyclobutadieneiron tricarbonyl is an example of metalloaromaticity, in which the Fe 3dxz and 3dyz orbitals interact with the π-system of cyclobutadiene to form a 4-membered aromatic ring in which electrons are delocalized outside the plane. This may be understood by considering the 2 d electrons of the metal as strongly interacting with the cyclobutadiene Pi system, such that there are 4n+2 electrons total. This aromaticity and equivalency of the C-C bonds has been characterized by NMR spectroscopy, x-ray crystallography, gas-phase electron diffraction, in which the C-C bonds are equivalent with an extremely low or nonexistent barrier to rotation. The C-C distances are 1.426 Å.[7] Additionally, the cyclobutadiene ligand may be understood as a sigma donor, interacting with the Metal dz2, s, and pz orbitals, and delta-accepting ligand, allowing for backbonding interactions from the dx2-y2 orbital. In the local symmetry of the CBDFe, three interactions are qualitatively depicted in figure 3.
Meanwhile, the bottom half of the compound features a tripodal carbonyl, making it an example of a piano stool complex. Here, the CO ligands are best classified as sigma donating and pi-acceptors, more strongly interacting with the dz2, dx2-y2 and dxy orbitals. Compared to traditional CO stretching frequencies, IR spectroscopy reveals two signals. In the local C3v symmetry of Fe(CO)3, these interactions are depicted.
Although formally the compound has a Cs symmetry, by examining the local symmetry of the ligands on the top and the bottom half of the molecule as C4v and C3v, ligand field theory can help understand the bonding as a perturbation on a C4H4Fe fragment by carbonyl ligands, indicating the unique nature of the CBDFe fragment. This can be especially contrasted with CpFe, in which Cp- is aromatic independent of its role as a metal ligand, in which both C-C bond distances are shorter and C-M bond distances are shorter in CpFe. Using aromaticity markers, researchers have even found that isolobal fragments to Fe(CO)3. CH+ and Be
Reactivity
[edit]Reactions not involving cyclobutadiene
Ligand substitution with dimethyl fumarate, dimethyl maleate, n-carboethoxyazepine, NO
dimerization,
Reactions that change cyclobutadiene
can change to eta 3, react with CF2=CF2
can react with ring expansion
reactions that only affect cyclobutadiene
can add COCH3, CHO, Ch2Cl, CH2NMe2, HgCl, D exchange, SO3H, COCCl3, COSMe for monosubstituted, which can then continue to transformed
di and polysubstituted, oxymercuration Cyclobutadieneiron tricarbonyl displays aromaticity as evidenced by some of its reactions, which can be classified as electrophilic aromatic substitution:[8]
It undergoes Friedel-Crafts acylation with acetyl chloride and aluminium chloride to give the acyl derivative 2, with formaldehyde and hydrochloric acid to the chloromethyl derivative 3, in a Vilsmeier-Haack reaction with N-methylformanilide and phosphorus oxychloride to the formyl 4, and in a Mannich reaction to amine derivative 5.
The reaction mechanism is identical to that of EAS:
Reactions that release cyclobutadiene
[edit]Oxidative decomplexation of cyclobutadiene is achieved by treating the tricarbonyl complex with ceric ammonium nitrate. The released cyclobutadiene is trapped with a quinone, which functions as a dienophile.[11]
can be trapped with various dienophiles
Uses and Applications
[edit]Solid-supported cyclobutadieneiron tricarbonyl complexes have been developed and evaluated for use in rapid and parallel synthesis of rigid rings[12]
Also led to a new synthesis of cubane, [13]
Metal-stabilized carbonium ions[14]
[2+2+1] intramolecular Pauson-Khand Type cycloaddition[15]
Oligomeric compounds[19]
radial cyclopentadienyl metals[20]
References
[edit]- ^ D. Seyferth "(Cyclobutadiene)iron Tricarbonyl - A Case of Theory before Experiment" Organometallics 2003, volume 22, 2-20.
- ^ Cyclobutadiene- and Benzocyclobutadiene-Iron Tricarbonyl Complexes G. F. Emerson, L. Watts, R. Pettit; J. Am. Chem. Soc.; 1965; 87(1); 131-133. First Page
- ^ Pettit, R.; Henery, J. (1970). "Cyclobutadieneiron Tricarbonyl". Organic Syntheses. 50: 21. doi:10.15227/orgsyn.050.0021.
- ^ Rosenblum, Myron.; Gatsonis, Christos. (1967-09). "New synthesis of cyclobutadiene iron tricarbonyl". Journal of the American Chemical Society. 89 (19): 5074–5075. doi:10.1021/ja00995a064. ISSN 0002-7863.
{{cite journal}}: Check date values in:|date=(help) - ^ a b Efraty, Avi. (1977-10-01). "Cyclobutadienemetal complexes". Chemical Reviews. 77 (5): 691–744. doi:10.1021/cr60309a003. ISSN 0009-2665.
- ^ King, R. B.; Haiduc, Ionel.; Eavenson, C. W. (1973-04). "Reactions of transition metal compounds with macrocyclic alkadiynes. III. Intramolecular transannular cyclizations and related processes with iron carbonyls". Journal of the American Chemical Society. 95 (8): 2508–2516. doi:10.1021/ja00789a016. ISSN 0002-7863.
{{cite journal}}: Check date values in:|date=(help) - ^ P. D. Harvey; W. P. Schaefer; H. B. Gray; D. F. R. Gilson; I. S. Butler (1988). "Structure of tricarbonyl(η4-cyclobutadienyl)iron(0) at −45 °C". Inorg. Chem. 27 (1): 57–59. doi:10.1021/ic00274a013.
- ^ Cyclobutadieneiron Tricarbonyl. A New Aromatic System J. D. Fitzpatrick, L. Watts, G. F. Emerson, R. Pettit J. Am. Chem. Soc.; 1965, vol. 87, 3254-3255 Abstract
- ^ Fujiwara, Yuzo; Asano, Ryuzo; Moritani, Ichiro; Teranishi, Shiichiro (1975-10-05). "AROMATIC SUBSTITUTION OF OLEFINS. REACTIONS OF NAPHTHALENE AND TRICARBONYL(η-CYCLOBUTADIENE) IRON(0) WITH STYRENE IN THE PRESENCE OF PALLADIUM(II) ACETATE". Chemistry Letters. 4 (10): 1061–1062. doi:10.1246/cl.1975.1061. ISSN 0366-7022.
- ^ Adams, Christopher M.; Crawford, Ellen S.; Salim, Eshragh (1992-07-07). "Intramolecular friedel-crafts acylation of a pendant chain cyclobutadiene complex: evidence for exo attack and formation of allyl-iron cations in cyclobutadiene tricarbonyliron". Tetrahedron Letters. 33 (28): 3963–3966. doi:10.1016/0040-4039(92)88073-E. ISSN 0040-4039.
- ^ "Cyclobutadiene In Synthesis: endo-Tricyclo[4.4.0.02,5]deca-3,8-diene-7,10-dione". Org. Synth. 55: 43. 1976. doi:10.15227/orgsyn.055.0043.
{{cite journal}}: Unknown parameter|authors=ignored (help) - ^ Marineau, Jason J.; Snapper, Marc L. (2012-06-11). "Development and Evaluation of a Solid-Supported Cyclobutadieneiron Tricarbonyl Complex for Parallel Synthesis Applications". ACS Combinatorial Science. 14 (6): 343–346. doi:10.1021/co2002069. ISSN 2156-8952.
- ^ Barborak, James C.; Watts, L.; Pettit, R. (1966-03). "A Convenient Synthesis of the Cubane System". Journal of the American Chemical Society. 88 (6): 1328–1329. doi:10.1021/ja00958a050. ISSN 0002-7863.
{{cite journal}}: Check date values in:|date=(help) - ^ Porter, James R.; Snapper, Marc L. (1999-08). "Formation of Carbon-Carbon Bonds Using Iron Tricarbonyl-(η4-cyclobutadienyl)-Stabilized Carbonium Ions". Synthesis. 1999 (S 01): 1407–1410. doi:10.1055/s-1999-3660. ISSN 0039-7881.
{{cite journal}}: Check date values in:|date=(help) - ^ Limanto, John; Tallarico, John A.; Porter, James R.; Khuong, Kelli S.; Houk, K. N.; Snapper, Marc L. (2002-12-01). "Intramolecular Cycloadditions of Cyclobutadiene with Olefins". Journal of the American Chemical Society. 124 (49): 14748–14758. doi:10.1021/ja0203162. ISSN 0002-7863.
- ^ Grubbs, Robert H.; Pancoast, Taylor A.; Grey, Roger A. (1974-01-01). "Intramolecular trapping of cyclobutadiene". Tetrahedron Letters. 15 (28): 2425–2426. doi:10.1016/S0040-4039(01)92275-0. ISSN 0040-4039.
- ^ Grubbs, Robert H.; Pancoast, Taylor A. (1977-03). "The mechanism of the oxidative decomposition of cyclobutadienyliron tricarbonyl complexes: intramolecular trapping". Journal of the American Chemical Society. 99 (7): 2382–2383. doi:10.1021/ja00449a081. ISSN 0002-7863.
{{cite journal}}: Check date values in:|date=(help) - ^ He, Jing; Snapper, Marc L. (2013-09-09). "New cycloaddition/fragmentation strategies for preparing 5-7-5 and 5-7-6 fused tricyclic ring systems". Tetrahedron. 2012 Tetrahedron Prize for Creativity in Organic Chemistry, Organic Synthesis: Applications to Biology, Medicine, and Materials, Paul A. Wender. 69 (36): 7831–7839. doi:10.1016/j.tet.2013.05.129. ISSN 0040-4020.
- ^ Bunz, Uwe H. F.; Wiegelmann‐Kreiter, Jutta E. C. (1996-07). "Cyclobutadiene Complexes, XII. Alkynyl‐Substituted Tricarbonyl(cyclobutadiene)iron Complexes: Stille Coupling of Iodocyclobutadiene Complexes with Stannylalkynes". Chemische Berichte. 129 (7): 785–797. doi:10.1002/cber.19961290709. ISSN 0009-2940.
{{cite journal}}: Check date values in:|date=(help) - ^ Eichberg, Michael J.; Kayser, Bernd; Leonard, Philip W.; Miljanić, Ognjen Š.; Timofeeva, Tatiana V.; Vollhardt, K. Peter C.; Whitener, Glenn D.; Yakovenko, Andrey; Yu, Yong (2011-04-15). "Radial (tetracyclopentadienyl)cyclobutadiene pentametals". Inorganica Chimica Acta. Special Volume: Protagonists in Chemistry Dedicated to Professor Robert G. Bergman. 369 (1): 32–39. doi:10.1016/j.ica.2010.10.004. ISSN 0020-1693.