In chemistry, a carbonium ion is a cation that has a pentacoordinated carbon atom. [2] They are a type of carbocation. In older literature, the name "carbonium ion" was used for what is today called carbenium. Carbonium ions charge is delocalized in three-center, two-electron bonds. The more stable members are often bi- or polycyclic. [3]
The 2-Norbornyl cation is one of the best characterized carbonium ion. It is the prototype for non-classical ions. As indicated first by low-temperature NMR spectroscopy and confirmed by X-ray crystallography, [1] it has a symmetric structure with an RCH2+ group bonded to an alkene group, stabilized by a bicyclic structure.
A non-classical structure for C
4H+
7 is supported by substantial experimental evidence from solvolysis experiments and NMR studies. One or both of two structures, the cyclopropylcarbinyl cation and the bicyclobutonium cation, were invoked to account for the observed reactivity. he NMR spectrum consists of two 13C NMR signals, even at temperatures as low as −132 °C. Computations suggest that the energetic landscape of the C
4H+
7 system is very flat. The bicyclobutonium structure is computed to be 0.4 kcal/mol more stable than the cyclopropylcarbinyl structure. In the solution phase (SbF5·SO2ClF·SO2F2, with SbF–
6 as the counterion), the bicyclobutonium structure predominates over the cyclopropylcarbinyl structure in a 84:16 ratio at −61 °C. Three other possible structures, two classical structures (the homoallyl cation and cyclobutyl cation) and a more highly delocalized non-classical structure (the tricyclobutonium ion), are less stable. [4]
The low temperature NMR spectrum of a dimethyl derivative shows two methyl signals, indicating that the molecular conformation of this cation is not perpendicular (as in A), which possesses a mirror plane, but is bisected (as in B) with the empty p-orbital parallel to the cyclopropyl ring system:
In terms of bent bond theory, this preference is explained by assuming favorable orbital overlap between the filled cyclopropane bent bonds and the empty p-orbital. [5]
The simplest carbonium ions are also the least accessible. In methanium (CH+5) carbon is covalently bonded to five hydrogen atoms. [6] [7] [8] [9]
The ethanium ion C2H+7 has been characterized by infrared spectroscopy. [10] The isomers of octonium (protonated octane, C8H+19) have been studied. [11]
| Pyramidal Carbocations | ||
|---|---|---|
 |  | One class of carbonium ions are called pyramidal carbocations. In these ions, a single carbon atom hovers over a four- or five-sided polygon, in effect forming a pyramid. The square pyramidal ion will carry a charge of +1, the Pentagonal pyramidal ion will carry +2. X-ray crystallography confirms that hexamethylbenzene dication ([C6(CH3)6]2+) is pentagonal-pyramidal. [12] |
| An example of the monovalent carbocation | An example of the divalent carbocation |
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Carbonium ions are intermediates in the isomerization of alkanes catalyzed by very strong solid acids. [13] Such carbonium ions are invoked in cracking (Haag-Dessau mechanism). [14] [15] [16]
In chemistry, hydronium (hydroxonium in traditional British English) is 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.
A carbocation is an ion with a positively charged carbon atom. Among the simplest examples are the methenium CH+
3, methanium CH+
5, acylium ions RCO+, and vinyl C
2H+
3 cations.
George Andrew Olah was a Hungarian-American chemist. His research involved the generation and reactivity of carbocations via superacids. For this research, Olah was awarded a Nobel Prize in Chemistry in 1994 "for his contribution to carbocation chemistry." He was also awarded the Priestley Medal, the highest honor granted by the American Chemical Society and F.A. Cotton Medal for Excellence in Chemical Research of the American Chemical Society in 1996.
Magic acid (FSO3H·SbF5) is a superacid consisting of a mixture, most commonly in a 1:1 molar ratio, of fluorosulfuric acid (HSO3F) and antimony pentafluoride (SbF5). This conjugate Brønsted–Lewis superacid system was developed in the 1960s by the George Olah lab at Case Western Reserve University, and has been used to stabilize carbocations and hypercoordinated carbonium ions in liquid media. Magic acid and other superacids are also used to catalyze isomerization of saturated hydrocarbons, and have been shown to protonate even weak bases, including methane, xenon, halogens, and molecular hydrogen.
A carbenium ion is a positive ion with the structure RR′R″C+, that is, a chemical species with carbon atom having three covalent bonds, and it bears a +1 formal charge. Carbenium ions are a major subset of carbocations, which is a general term for diamagnetic carbon-based cations. In parallel with carbenium ions is another subset of carbocations, the carbonium ions with the formula R5+. In carbenium ions charge is localized. They are isoelectronic with monoboranes such as B(CH3)3.
Fluoroantimonic acid is a mixture of hydrogen fluoride and antimony pentafluoride, containing various cations and anions. This mixture is a superacid that, in terms of corrosiveness, is trillions of times stronger than pure sulfuric acid when measured by its Hammett acidity function. It even protonates some hydrocarbons to afford pentacoordinate carbocations. Like its precursor hydrogen fluoride, it attacks glass, but can be stored in containers lined with PTFE (Teflon) or PFA.
In organic chemistry, the term 2-norbornyl cation describes a carbonium ionic derivative of norbornane. A salt of the 2-norbornyl cation was crystallized and characterized by X-ray crystallography confirmed the non-classical structure.
Homoaromaticity, in organic chemistry, refers to a special case of aromaticity in which conjugation is interrupted by a single sp3 hybridized carbon atom. Although this sp3 center disrupts the continuous overlap of p-orbitals, traditionally thought to be a requirement for aromaticity, considerable thermodynamic stability and many of the spectroscopic, magnetic, and chemical properties associated with aromatic compounds are still observed for such compounds. This formal discontinuity is apparently bridged by p-orbital overlap, maintaining a contiguous cycle of π electrons that is responsible for this preserved chemical stability.
In chemistry, methanium is a complex positive ion with formula [CH5]+ or [CH3(H2)]+, bearing a +1 electric charge. It is a superacid and one of the onium ions, indeed the simplest carbonium ion.
In chemistry, an onium ion is a cation formally obtained by the protonation of mononuclear parent hydride of a pnictogen, chalcogen, or halogen. The oldest-known onium ion, and the namesake for the class, is ammonium, NH+4, the protonated derivative of ammonia, NH3.
In chemistry and molecular physics, fluxionalmolecules are molecules that undergo dynamics such that some or all of their atoms interchange between symmetry-equivalent positions. Because virtually all molecules are fluxional in some respects, e.g. bond rotations in most organic compounds, the term fluxional depends on the context and the method used to assess the dynamics. Often, a molecule is considered fluxional if its spectroscopic signature exhibits line-broadening due to chemical exchange. In some cases, where the rates are slow, fluxionality is not detected spectroscopically, but by isotopic labeling and other methods.
The helium hydride ion, hydridohelium(1+) ion, or helonium is a cation (positively charged ion) with chemical formula HeH+. It consists of a helium atom bonded to a hydrogen atom, with one electron removed. It can also be viewed as protonated helium. It is the lightest heteronuclear ion, and is believed to be the first compound formed in the Universe after the Big Bang.
In chemistry, a nonclassical ion usually refers to carbonium ions, a family of organic cations. They are characterized by delocalized three-center, two-electron bonds. The more stable members are often bi- or polycyclic.
In chemistry, ethanium or protonated ethane is a highly reactive positive ion with formula C
2H+
7. It can be described as a molecule of ethane with one extra proton, that gives it a +1 electric charge.
In organic chemistry, methenium is a cation with the formula CH+
3. It can be viewed as a methylene radical with an added proton, or as a methyl radical with one electron removed. It is a carbocation and an enium ion, making it the simplest of the carbenium ions.
Dioxidanylium, which is protonated molecular oxygen, or just protonated oxygen, is an ion with formula HO+
2. It is formed when hydrogen containing substances combust, and exists in the ionosphere, and in plasmas that contain oxygen and hydrogen. Oxidation by O2 in superacids could be by way of the production of protonated molecular oxygen.
Argon compounds, the chemical compounds that contain the element argon, are rarely encountered due to the inertness of the argon atom. However, compounds of argon have been detected in inert gas matrix isolation, cold gases, and plasmas, and molecular ions containing argon have been made and also detected in space. One solid interstitial compound of argon, Ar1C60 is stable at room temperature. Ar1C60 was discovered by the CSIRO.
Hydrogen-bridged cations are a type of charged species in which a hydrogen atom is simultaneously bonded to two atoms through partial sigma bonds. While best observable in the presence of superacids at room temperature, spectroscopic evidence has suggested that hydrogen-bridged cations exist in ordinary solvents. These ions have been the subject of debate as they constitute a type of charged species of uncertain electronic structure.
In chemistry, the decay technique is a method to generate chemical species such as radicals, carbocations, and other potentially unstable covalent structures by radioactive decay of other compounds. For example, decay of a tritium-labeled molecule yields an ionized helium atom, which might then break off to leave a cationic molecular fragment.
Nitrogen pentahydride, also known as ammonium hydride is a hypothetical compound with the chemical formula NH5. There are two theoretical structures of nitrogen pentahydride. One structure is trigonal bipyramidal molecular geometry type NH5 molecule. Its nitrogen atom and hydrogen atoms are covalently bounded, and its symmetry group is D3h. Another predicted structure of nitrogen pentahydride is an ionic compound, composed of an ammonium ion and a hydride ion (NH4+H−). Until now, no one has synthesized this substance, or proved its existence, and related experiments have not directly observed nitrogen pentahydride. It is only speculated that it may be a reactive intermediate based on reaction products. Theoretical calculations show this molecule is thermodynamically unstable. The reason might be similar to the instability of nitrogen pentafluoride, so the possibility of its existence is low. However, nitrogen pentahydride might exist in special conditions or high pressure. Nitrogen pentahydride was considered for use as a solid rocket fuel for research in 1966.