organic chemistry Organic chemistry is a subdiscipline within chemistry involving the scientific study of the structure, properties, and reactions of organic compounds and organic materials, i.e., matter in its various forms that contain carbon atoms.Clayden, J.; ...

, the tropylium ion or cycloheptatrienyl cation is an

aromatic In chemistry, aromaticity is a chemical property of cyclic ( ring-shaped), ''typically'' planar (flat) molecular structures with pi bonds in resonance (those containing delocalized electrons) that gives increased stability compared to satur ...

species with a formula of ₇H₇sup>+. Its name derives from the molecule

tropine Tropine is a derivative of tropane containing a hydroxyl group at the third carbon. It is also called 3-tropanol. Tropine is a central building block of many chemicals active in the nervous system, including tropane alkaloids. Some of these comp ...

from which

cycloheptatriene 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 inter ...

(tropylidene) was first synthesized in 1881. Salts of the tropylium cation can be stable, even with nucleophiles of moderate strength e.g.,

tropylium tetrafluoroborate Tropylium tetrafluoroborate is an organic compound with the formula C7H7BF4. Containing the tropylium cation and the non-coordinating tetrafluoroborate counteranion, tropylium tetrafluoroborate is a rare example of a readily isolable carbocation. ...

and tropylium bromide (''see below''). Its bromide and chloride salts can be made from cycloheptatriene and

bromine Bromine is a chemical element with the symbol Br and atomic number 35. It is the third-lightest element in group 17 of the periodic table (halogens) and is a volatile red-brown liquid at room temperature that evaporates readily to form a simila ...

phosphorus pentachloride Phosphorus pentachloride is the chemical compound with the formula PCl5. It is one of the most important phosphorus chlorides, others being PCl3 and POCl3. PCl5 finds use as a chlorinating reagent. It is a colourless, water-sensitive and moist ...

, respectively. It is a regular

heptagon In geometry, a heptagon or septagon is a seven-sided polygon or 7-gon. The heptagon is sometimes referred to as the septagon, using "sept-" (an elision of ''septua-'', a Latin-derived numerical prefix, rather than ''hepta-'', a Greek-derived num ...

al, planar, cyclic ion. It has 6 π-electrons (4''n'' + 2, where ''n'' = 1), which fulfills

Hückel's rule In organic chemistry, Hückel's rule predicts that a planar ring molecule will have aromatic properties if it has 4''n'' + 2 π electrons, where ''n'' is a non-negative integer. The quantum mechanical basis for its formulation was fir ...

of aromaticity. It can coordinate as a

ligand In coordination chemistry, a ligand is an ion or molecule (functional group) that binds to a central metal atom to form a coordination complex. The bonding with the metal generally involves formal donation of one or more of the ligand's electr ...

metal A metal (from Greek μέταλλον ''métallon'', "mine, quarry, metal") is a material that, when freshly prepared, polished, or fractured, shows a lustrous appearance, and conducts electricity and heat relatively well. Metals are typicall ...

atoms Every atom is composed of a nucleus and one or more electrons bound to the nucleus. The nucleus is made of one or more protons and a number of neutrons. Only the most common variety of hydrogen has no neutrons. Every solid, liquid, gas, an ...

. The structure shown is a composite of seven

resonance contributor In chemistry, resonance, also called mesomerism, is a way of describing bonding in certain molecules or polyatomic ions by the combination of several contributing structures (or ''forms'', also variously known as ''resonance structures'' or ...

s 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

and

. Unlike most hydrocarbyl 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, , by Doering and Knox in 1954 by analysis of its infrared and ultraviolet spectra. The ionic structures of tropylium perchlorate () and tropylium iodide () have been confirmed by

X-ray crystallography X-ray crystallography is the experimental science determining the atomic and molecular structure of a crystal, in which the crystalline structure causes a beam of incident X-rays to diffract into many specific directions. By measuring the angles ...

. The bond length of the carbon-carbon bonds is longer (147 pm) than those of

benzene Benzene is an organic chemical compound with the molecular formula C6H6. The benzene molecule is composed of six carbon atoms joined in a planar ring with one hydrogen atom attached to each. Because it contains only carbon and hydrogen atoms, ...

(140 pm) but still shorter than those of a typical single-bonded species like

ethane Ethane ( , ) is an organic chemical compound with chemical formula . At standard temperature and pressure, ethane is a colorless, odorless gas. Like many hydrocarbons, ethane is isolated on an industrial scale from natural gas and as a petr ...

(154 pm).

Acidity

The tropylium ion is an acid in aqueous solution (i.e., an

Arrhenius acid Arrhenius may refer to * Birgit Arrhenius (born 1932), Swedish archaeologist * Carl Axel Arrhenius (1757–1824), Swedish army lieutenant and amateur mineralogist who discovered ytterbite, a mineral that led to the discovery of yttrium by Johan Gado ...

) 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: : + 2 + (

Boric acid Boric acid, more specifically orthoboric acid, is a compound of boron, oxygen, and hydrogen with formula . It may also be called hydrogen borate or boracic acid. It is usually encountered as colorless crystals or a white powder, that dissolves ...

gives acidic aqueous solutions in much the same way.) The equilibrium constant is , making it about as acidic in water as

acetic acid Acetic acid , systematically named ethanoic acid , is an acidic, colourless liquid and organic compound with the chemical formula (also written as , , or ). Vinegar is at least 4% acetic acid by volume, making acetic acid the main component ...

Mass spectrometry

The tropylium ion is frequently encountered in

mass spectrometry Mass spectrometry (MS) is an analytical technique that is used to measure the mass-to-charge ratio of ions. The results are presented as a ''mass spectrum'', a plot of intensity as a function of the mass-to-charge ratio. Mass spectrometry is use ...

in the form of a signal at ''m''/''z'' = 91 and is used in

mass spectrum analysis Mass spectral interpretation is the method employed to identify the chemical formula, characteristic fragment patterns and possible fragment ions from the mass spectra. Mass spectra is a plot of relative abundance against mass-to-charge ratio. It i ...

. This fragment is often found for aromatic compounds containing a benzyl unit. Upon

ionization Ionization, or Ionisation is the process by which an atom or a molecule acquires a negative or positive charge by gaining or losing electrons, often in conjunction with other chemical changes. The resulting electrically charged atom or molecule i ...

, the benzyl fragment forms a cation (), which rearranges to the highly stable tropylium cation ().

Reactions

The tropylium cation reacts with nucleophiles to form substituted cycloheptatrienes, for example: : + → Reduction by

lithium aluminum hydride Lithium aluminium hydride, commonly abbreviated to LAH, is an inorganic compound with the chemical formula Li Al H4. It is a white solid, discovered by Finholt, Bond and Schlesinger in 1947. This compound is used as a reducing agent in organic sy ...

yields

. Reaction with a

cyclopentadienide In chemistry, the cyclopentadienyl anion or cyclopentadienide is an aromatic species with a formula of and abbreviated as Cp−. It is formed from the deprotonation of the molecule cyclopentadiene. Properties The cyclopentadienyl anion i ...

salt of

sodium Sodium is a chemical element with the symbol Na (from Latin ''natrium'') and atomic number 11. It is a soft, silvery-white, highly reactive metal. Sodium is an alkali metal, being in group 1 of the periodic table. Its only stable iso ...

lithium Lithium (from el, λίθος, lithos, lit=stone) is a chemical element with the symbol Li and atomic number 3. It is a soft, silvery-white alkali metal. Under standard conditions, it is the least dense metal and the least dense solid el ...

yields 7-cyclopentadienylcyclohepta-1,3,5-triene: : + → + When treated with oxidising agents such as

chromic acid The term chromic acid is usually used for a mixture made by adding concentrated sulfuric acid to a dichromate, which may contain a variety of compounds, including solid chromium trioxide. This kind of chromic acid may be used as a cleaning mixt ...

, the tropylium cation undergoes rearrangement into

benzaldehyde Benzaldehyde (C6H5CHO) is an organic compound consisting of a benzene ring with a formyl substituent. It is the simplest aromatic aldehyde and one of the most industrially useful. It is a colorless liquid with a characteristic almond-like odor. ...

: : + → + + Many metal complexes of tropylium ion are known. One example is o(''η''⁷-C₇H₇)(CO)₃sup>+, which is prepared by hydride abstraction from cycloheptatrienemolybdenum tricarbonyl.

References

{{Reflist Simple aromatic rings Cations Carbocations Non-benzenoid aromatic carbocycles Cycloheptatrienyl complexes de:Tropylium

History

Acidity

Mass spectrometry

Reactions

See also

References