Tropylium cation

Last updated
Tropylium [1]
Tropylium.svg
Tropylium-ion-3D-balls.png
Tropylium-ion-3D-vdW.png
Names
Preferred IUPAC name
Cycloheptatrienylium [2]
Other names
cyc-C
7
H+
7
, Cyclohepta-2,4,6-trienylium, [3] [1] Cyclohepta-1,3,5-triene, [3] 2,4,6-Cycloheptatrienylium [1]
Identifiers
3D model (JSmol)
1902352 [1]
ChemSpider
PubChem CID
  • InChI=1S/C7H7/c1-2-4-6-7-5-3-1/h1-7H/q+1
    Key: OJOSABWCUVCSTQ-UHFFFAOYSA-N [1]
  • [3] :InChI=1S/C7H7/c1-2-4-6-7-5-3-1/h1-7H/q+1
    Key: OJOSABWCUVCSTQ-UHFFFAOYSA-N [3]
  • c1=cc=c[cH+]c=c1
Properties
C
7
H+
7
[3]
Molar mass 91.132 g·mol−1
Structure
D7h
regular heptagon
Related compounds
Other anions
Tropylium tetrafluoroborate
Except where otherwise noted, data are given for materials in their standard state (at 25 °C [77 °F], 100 kPa).

The tropylium ion or cycloheptatrienyl cation is an aromatic species with a formula of [C7H7]+. [4] Its name derives from the molecule tropine from which cycloheptatriene (tropylidene) was first synthesized in 1881. Salts of the tropylium cation can be stable, even with nucleophiles of moderate strength e.g., tropylium tetrafluoroborate and tropylium bromide (see below). Its bromide and chloride salts [5] can be made from cycloheptatriene and bromine or phosphorus pentachloride, respectively. [6]

Contents

It is a regular heptagonal, planar, cyclic ion. It has 6 π-electrons (4n + 2, where n = 1), which fulfills Hückel's rule of aromaticity. It can coordinate as a ligand to metal atoms. The structure shown is a composite of seven resonance contributors in which each carbon atom carries part of the positive charge.

History

In 1891 G. Merling obtained a water-soluble bromine-containing compound from the reaction of cycloheptatriene and bromine. [7] Unlike most alkyl bromides, this compound, later named tropylium bromide, is water-soluble but insoluble in many organic solvents. It is purified by crystallization from hot ethanol. Reaction with aqueous silver nitrate immediately gave silver bromide, indicating labile bromide. Tropylium bromide was deduced to be a salt, C
7
H+
7
Br
, by Doering and Knox in 1954 by analysis of its infrared and ultraviolet spectra. [8] [9] The ionic structures of tropylium perchlorate (C
7
H+
7
ClO
4
) and tropylium iodide (C
7
H+
7
I
) have been confirmed by X-ray crystallography. [10] The bond length of the carbon-carbon bonds is longer (147 pm) than those of benzene (140 pm) but still shorter than those of a typical single-bonded species like ethane (154 pm).

Acidity

The tropylium ion is an acid in aqueous solution (i.e., an Arrhenius acid) as a consequence of its Lewis acidity: it first acts as a Lewis acid to form an adduct with water, which can then donate a proton to another molecule of water, therefore indirectly acting as an Arrhenius acid:

C
7
H+
7
+ 2 H
2
O
C
7
H
7
OH
+ H
3
O+

(Boric acid gives acidic aqueous solutions in much the same way.) The equilibrium constant is 1.8×10−5, making it about as acidic in water as acetic acid. [8]

Mass spectrometry

The tropylium ion is frequently encountered in mass spectrometry in the form of a signal at m/z  = 91 and is used in mass spectrum analysis. This fragment is often found for aromatic compounds containing a benzyl unit. Upon ionization, the benzyl fragment forms a cation (PhCH+
2
), which rearranges to the highly stable tropylium cation (C
7
H+
7
). [11]

Reactions

The tropylium cation reacts with nucleophiles to form substituted cycloheptatrienes, for example: [12]

C
7
H+
7
+ CN
C
7
H
7
CN

Reduction by lithium aluminium hydride yields cycloheptatriene. [12]

Reaction with a cyclopentadienide salt of sodium or lithium yields 7-cyclopentadienylcyclohepta-1,3,5-triene: [12]

C
7
H+
7
X
+ C
5
H
5
Na+
C
7
H
7
C
5
H
5
+ NaX

When treated with oxidising agents such as chromic acid, the tropylium cation undergoes rearrangement into benzaldehyde: [12]

C
7
H+
7
+ HCrO
4
C
6
H
5
CHO
+ CrO
2
+ H
2
O

Many metal complexes of tropylium ion are known. One example is [Mo(η7-C7H7)(CO)3]+, which is prepared by hydride abstraction from cycloheptatrienemolybdenum tricarbonyl. [13]

See also

Related Research Articles

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Bromine is a chemical element; it has symbol Br and atomic number 35. It is a volatile red-brown liquid at room temperature that evaporates readily to form a similarly coloured vapour. Its properties are intermediate between those of chlorine and iodine. Isolated independently by two chemists, Carl Jacob Löwig and Antoine Jérôme Balard, its name was derived from the Ancient Greek βρῶμος (bromos) meaning "stench", referring to its sharp and pungent smell.

In chemistry, a nucleophile is a chemical species that forms bonds by donating an electron pair. All molecules and ions with a free pair of electrons or at least one pi bond can act as nucleophiles. Because nucleophiles donate electrons, they are Lewis bases.

In chemistry, hydronium (hydroxonium in traditional British English) is the common name for the cation [H3O]+, also written as H3O+, the type of oxonium ion produced by protonation of water. It is often viewed as the positive ion present when an Arrhenius acid is dissolved in water, as Arrhenius acid molecules in solution give up a proton (a positive hydrogen ion, H+) to the surrounding water molecules (H2O). In fact, acids must be surrounded by more than a single water molecule in order to ionize, yielding aqueous H+ and conjugate base. Three main structures for the aqueous proton have garnered experimental support: the Eigen cation, which is a tetrahydrate, H3O+(H2O)3, the Zundel cation, which is a symmetric dihydrate, H+(H2O)2, and the Stoyanov cation, an expanded Zundel cation, which is a hexahydrate: H+(H2O)2(H2O)4. Spectroscopic evidence from well-defined IR spectra overwhelmingly supports the Stoyanov cation as the predominant form. For this reason, it has been suggested that wherever possible, the symbol H+(aq) should be used instead of the hydronium ion.

<span class="mw-page-title-main">Haloalkane</span> Group of chemical compounds derived from alkanes containing one or more halogens

The haloalkanes are alkanes containing one or more halogen substituents. They are a subset of the general class of halocarbons, although the distinction is not often made. Haloalkanes are widely used commercially. They are used as flame retardants, fire extinguishants, refrigerants, propellants, solvents, and pharmaceuticals. Subsequent to the widespread use in commerce, many halocarbons have also been shown to be serious pollutants and toxins. For example, the chlorofluorocarbons have been shown to lead to ozone depletion. Methyl bromide is a controversial fumigant. Only haloalkanes that contain chlorine, bromine, and iodine are a threat to the ozone layer, but fluorinated volatile haloalkanes in theory may have activity as greenhouse gases. Methyl iodide, a naturally occurring substance, however, does not have ozone-depleting properties and the United States Environmental Protection Agency has designated the compound a non-ozone layer depleter. For more information, see Halomethane. Haloalkane or alkyl halides are the compounds which have the general formula "RX" where R is an alkyl or substituted alkyl group and X is a halogen.

<span class="mw-page-title-main">Carbocation</span> Ion with a positively charged carbon atom

A carbocation is an ion with a positively charged carbon atom. Among the simplest examples are the methenium CH+
3
, methanium CH+
5
and vinyl C
2
H+
3
cations. Occasionally, carbocations that bear more than one positively charged carbon atom are also encountered.

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Cycloheptatriene (CHT) is an organic compound with the formula C7H8. It is a closed ring of seven carbon atoms joined by three double bonds (as the name implies) and four single bonds. This colourless liquid has been of recurring theoretical interest in organic chemistry. It is a ligand in organometallic chemistry and a building block in organic synthesis. Cycloheptatriene is not aromatic, as reflected by the nonplanarity of the methylene bridge (-CH2-) with respect to the other atoms; however the related tropylium cation is.

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References

  1. 1 2 3 4 5 6 "tropylium | ChemSpider". www.chemspider.com. p. Names. Retrieved 30 December 2018. tropylium
  2. International Union of Pure and Applied Chemistry (2014). Nomenclature of Organic Chemistry: IUPAC Recommendations and Preferred Names 2013. The Royal Society of Chemistry. p. 1127. doi:10.1039/9781849733069. ISBN   978-0-85404-182-4.
  3. 1 2 3 4 5 6 "Tropylium". pubchem.ncbi.nlm.nih.gov. Retrieved 30 December 2018. Chemical Names: Tropylium; Cycloheptatrienylium; Cyc-C
    7
    H+
    7
    ; Cyclohepta-2,4,6-trienylium
  4. IUPAC , Compendium of Chemical Terminology , 2nd ed. (the "Gold Book") (1997). Online corrected version: (2006) " molecule ". doi : 10.1351/goldbook.M04002
  5. A mixture of [C7H7]+Cl and [C7H7]+[PCl
    6
    ] is produced by treatment of tropylidene with phosphorus pentachloride.
  6. Tropylium fluoborate Organic Syntheses, Coll. Vol. 5, p.1138 (1973); Vol. 43, p.101 (1963). link Archived 2012-08-29 at the Wayback Machine
  7. Merling, G. (1891). "Ueber Tropin". Berichte der Deutschen Chemischen Gesellschaft. 24 (2): 3108–3126. doi:10.1002/cber.189102402151.
  8. 1 2 Eggers Doering, W. von; Knox, L. H. (1954). "The Cycloheptatrienylium (Tropylium) Ion". J. Am. Chem. Soc. 76 (12): 3203–3206. doi:10.1021/ja01641a027.
  9. Balaban, Alexandru T.; Oniciu, Daniela C.; Katritzky, Alan R. (2004). "Aromaticity as a Cornerstone of Heterocyclic Chemistry". Chem. Rev. 104 (5): 2777–2812. doi:10.1021/cr0306790. PMID   15137807.
  10. Kitaigorodskii, A. I.; Struchkov, Yu. T.; Khotsyanova, T. L.; Vol'pin, M. E.; Kursanov, D. N. (1960). "Crystal structures of tropylium perchlorate and iodide". Bulletin of the Academy of Sciences of the USSR Division of Chemical Science. 9 (1): 32–36. doi:10.1007/bf01178699. ISSN   0568-5230.
  11. Lifshitz, Chava (1994). "Tropylium Ion Formation from Toluene: Solution of an Old Problem in Organic Mass Spectrometry". Accounts of Chemical Research. 27 (5): 138–144. doi:10.1021/ar00041a004.
  12. 1 2 3 4 O. P. Agarwai (2009). Reactions and Reagents (46th ed.). Krishna Prakashan Media. pp. 614–615. ISBN   978-81-87224-65-5.
  13. Green, Malcolm L. H.; Ng, Dennis K. P. (1995). "Cycloheptatriene and -enyl Complexes of the Early Transition Metals". Chemical Reviews. 95 (2): 439–473. doi:10.1021/cr00034a006.