Halonium ion

Last updated
A ball-and-stick model of a bromonium ion formed from cyclopentene Cyclopentene-bromonium-3D-balls.png
A ball-and-stick model of a bromonium ion formed from cyclopentene

A halonium ion is any onium ion containing a halogen atom carrying a positive charge. This cation has the general structure R−+X−R′ where X is any halogen and no restrictions on R, [1] this structure can be cyclic or an open chain molecular structure. Halonium ions formed from fluorine, chlorine, bromine, and iodine are called fluoronium , chloronium, bromonium, and iodonium, respectively. [1] The 3-membered cyclic variety commonly proposed as intermediates in electrophilic halogenation may be called haliranium ions, using the Hantzsch-Widman nomenclature system.

Contents

Structure

The simplest halonium ions are of the structure H−+X−H (X = F, Cl, Br, I). Many halonium ions have a three-atom cyclic structure, similar to that of an epoxide, resulting from the formal addition of a halogenium ion X+ to a C=C double bond, as when a halogen is added to an alkene. [1] The formation of 5-membered halonium ions (e.g., chlorolanium, bromolanium ions) via neighboring group participation is also well studied. [2]

Diaryliodonium ions ([Ar2I]+X−) are generally stable, isolable salts which exhibit a T-shaped geometry with the aryl groups at ~90 degrees apart; [3] for more details, see hypervalent iodine.

The tendency to form bridging halonium ions is in the order I > Br > Cl > F. Whereas iodine and bromine readily form bridged iodonium and bromonium ions, fluoronium ions have only recently been characterized in designed systems that force close encounter of the fluorine lone pair and a carbocationic center. In practice, structurally, there is a continuum between a symmetrically bridged halonium, to an unsymmetrical halonium with a long weak bond to one of the carbon centers, to a true β-halocarbocation with no halonium character. The equilibrium structure depends on the ability of the carbon atoms and the halogen to accommodate positive charge. Thus, a bromonium ion that bridges a primary and tertiary carbon will often exhibit a skewed structure, with a weak bond to the tertiary center (with significant carbocation character) and stronger bond to the primary carbon. This is due to the increased stability of tertiary carbons to stabilize positive charge. In the more extreme case, if the tertiary center is doubly benzylic for instance, then the open form may be favored. Similarly, switching from bromine to chlorine also weakens bridging character, due to the higher electronegativity of chlorine and lower propensity to share electron density compared to bromine.

Reactivity

These ions are usually only short-lived reaction intermediates; they are very reactive, owing to high ring strain in the three-membered ring and the positive charge on the halogen; this positive charge makes them great electrophiles. In almost all cases, the halonium ion is attacked by a nucleophile within a very short time. Even a weak nucleophile, such as water will attack the halonium ion; this is how halohydrins can be made.

On occasion, a halonium atom will rearrange to a carbocation. This usually occurs only when that carbocation is an allylic or a benzylic carbocation. [4]

History

Halonium ions were first postulated in 1937 by Roberts and Kimball [5] to account for observed anti diastereoselectivity in halogen addition reactions to alkenes. They correctly argued that if the initial reaction intermediate in bromination is the open-chain X–C–C+ species, rotation around the C–C single bond would be possible leading to a mixture of equal amounts of dihalogen syn isomer and anti isomer, which is not the case. They also asserted that a positively charged halogen atom is isoelectronic with oxygen and that carbon and bromine have comparable ionization potentials. For certain aryl substituted alkenes, the anti stereospecificity is diminished or lost, as a result of weakened or absent halonium character in the cationic intermediate.

In 1970 George A. Olah succeeded in preparing and isolating halonium salts [6] by adding a methyl halide such as methyl bromide or methyl chloride in sulfur dioxide at −78 °C to a complex of antimony pentafluoride and tetrafluoromethane in sulfur dioxide. After evaporation of sulfur dioxide this procedure left crystals of [H3C–+X–CH3][SbF6]–, stable at room temperature but not to moisture. A fluoronium ion was recently characterized in solution phase (dissolved in sulfur dioxide or sulfuryl chloride fluoride) at low temperature. [7]

Cyclic and acyclic chloronium, [8] bromonium, and iodonium ions have been structurally characterised by X-ray crystallography, such as the bi(adamantylidene)-derived bromonium cation shown below. [9]

Biadamantylidene-bromonium-ion-from-xtal-1994-2D-skeletal.png
Biadamantylidene-bromonium-ion-from-xtal-1994-3D-balls.png
skeletal formula ball-and-stick model

Compounds containing trivalent or tetravalent halonium ions do not exist but for some hypothetical compounds stability has been computationally tested. [10]

Related Research Articles

<span class="mw-page-title-main">Alkene</span> Hydrocarbon compound containing one or more C=C bonds

In organic chemistry, an alkene is a hydrocarbon containing a carbon–carbon double bond. The double bond may be internal or in the terminal position. Terminal alkenes are also known as α-olefins.

<span class="mw-page-title-main">Bromine</span> Chemical element, symbol Br and atomic number 35

Bromine is a chemical element with the 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.

<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.

In organic chemistry, Markovnikov's rule or Markownikoff's rule describes the outcome of some addition reactions. The rule was formulated by Russian chemist Vladimir Markovnikov in 1870.

A halogen addition reaction is a simple organic reaction where a halogen molecule is added to the carbon–carbon double bond of an alkene functional group.

<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
2H+
3 cations. Occasionally, carbocations that bear more than one positively charged carbon atom are also encountered.

In chemistry, an electrophile is a chemical species that forms bonds with nucleophiles by accepting an electron pair. Because electrophiles accept electrons, they are Lewis acids. Most electrophiles are positively charged, have an atom that carries a partial positive charge, or have an atom that does not have an octet of electrons.

In chemistry, halogenation is a chemical reaction that entails the introduction of one or more halogens into a compound. Halide-containing compounds are pervasive, making this type of transformation important, e.g. in the production of polymers, drugs. This kind of conversion is in fact so common that a comprehensive overview is challenging. This article mainly deals with halogenation using elemental halogens (F2, Cl2, Br2, I2). Halides are also commonly introduced using salts of the halides and halogen acids. Many specialized reagents exist for and introducing halogens into diverse substrates, e.g. thionyl chloride.

In chemistry, an interhalogen compound is a molecule which contains two or more different halogen atoms and no atoms of elements from any other group.

In organic chemistry, an electrophilic aromatic halogenation is a type of electrophilic aromatic substitution. This organic reaction is typical of aromatic compounds and a very useful method for adding substituents to an aromatic system.

<span class="mw-page-title-main">Hydrohalogenation</span> Electrophilic addition of hydrohalic acids to alkenes

A hydrohalogenation reaction is the electrophilic addition of hydrohalic acids like hydrogen chloride or hydrogen bromide to alkenes to yield the corresponding haloalkanes.

<span class="mw-page-title-main">Carbenium ion</span> Class of ions

A carbenium ion is a positive ion with the structure RR′R″C+, that is, a chemical species with a trivalent carbon that bears a +1 formal charge.

<span class="mw-page-title-main">Prins reaction</span> Chemical reaction involving organic compounds

The Prins reaction is an organic reaction consisting of an electrophilic addition of an aldehyde or ketone to an alkene or alkyne followed by capture of a nucleophile or elimination of an H+ ion. The outcome of the reaction depends on reaction conditions. With water and a protic acid such as sulfuric acid as the reaction medium and formaldehyde the reaction product is a 1,3-diol (3). When water is absent, the cationic intermediate loses a proton to give an allylic alcohol (4). With an excess of formaldehyde and a low reaction temperature the reaction product is a dioxane (5). When water is replaced by acetic acid the corresponding esters are formed.

Bromine compounds are compounds containing the element bromine (Br). These compounds usually form the -1, +1, +3 and +5 oxidation states. Bromine is intermediate in reactivity between chlorine and iodine, and is one of the most reactive elements. Bond energies to bromine tend to be lower than those to chlorine but higher than those to iodine, and bromine is a weaker oxidising agent than chlorine but a stronger one than iodine. This can be seen from the standard electrode potentials of the X2/X− couples (F, +2.866 V; Cl, +1.395 V; Br, +1.087 V; I, +0.615 V; At, approximately +0.3 V). Bromination often leads to higher oxidation states than iodination but lower or equal oxidation states to chlorination. Bromine tends to react with compounds including M–M, M–H, or M–C bonds to form M–Br bonds.

Iodine can form compounds using multiple oxidation states. Iodine is quite reactive, but it is much less reactive than the other halogens. For example, while chlorine gas will halogenate carbon monoxide, nitric oxide, and sulfur dioxide, iodine will not do so. Furthermore, iodination of metals tends to result in lower oxidation states than chlorination or bromination; for example, rhenium metal reacts with chlorine to form rhenium hexachloride, but with bromine it forms only rhenium pentabromide and iodine can achieve only rhenium tetraiodide. By the same token, however, since iodine has the lowest ionisation energy among the halogens and is the most easily oxidised of them, it has a more significant cationic chemistry and its higher oxidation states are rather more stable than those of bromine and chlorine, for example in iodine heptafluoride.

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.

<span class="mw-page-title-main">Carbon–fluorine bond</span> Covalent bond between carbon and fluorine atoms

The carbon–fluorine bond is a polar covalent bond between carbon and fluorine that is a component of all organofluorine compounds. It is one of the strongest single bonds in chemistry, and relatively short, due to its partial ionic character. The bond also strengthens and shortens as more fluorines are added to the same carbon on a chemical compound. As such, fluoroalkanes like tetrafluoromethane are some of the most unreactive organic compounds.

The Hofmann–Löffler reaction (also referred to as Hofmann–Löffler–Freytag reaction, Löffler–Freytag reaction, Löffler–Hofmann reaction, as well as Löffler's method) is an organic reaction in which a cyclic amine 2 (pyrrolidine or, in some cases, piperidine) is generated by thermal or photochemical decomposition of N-halogenated amine 1 in the presence of a strong acid (concentrated sulfuric acid or concentrated CF3CO2H). The Hofmann–Löffler–Freytag reaction proceeds via an intramolecular hydrogen atom transfer to a nitrogen-centered radical and is an example of a remote intramolecular free radical C–H functionalization.

<span class="mw-page-title-main">Vinyl cation</span> Organic cation

The vinyl cation is a carbocation with the positive charge on an alkene carbon. Its empirical formula is C
2H+
3. More generally, a vinylic cation is any disubstituted, trivalent carbon, where the carbon bearing the positive charge is part of a double bond and is sp hybridized. In the chemical literature, substituted vinylic cations are often referred to as vinyl cations, and understood to refer to the broad class rather than the C
2H+
3 variant alone. The vinyl cation is one of the main types of reactive intermediates involving a non-tetrahedrally coordinated carbon atom, and is necessary to explain a wide variety of observed reactivity trends. Vinyl cations are observed as reactive intermediates in solvolysis reactions, as well during electrophilic addition to alkynes, for example, through protonation of an alkyne by a strong acid. As expected from its sp hybridization, the vinyl cation prefers a linear geometry. Compounds related to the vinyl cation include allylic carbocations and benzylic carbocations, as well as aryl carbocations.

In chemistry, molecular oxohalides (oxyhalides) are a group of chemical compounds in which both oxygen and halogen atoms are attached to another chemical element A in a single molecule. They have the general formula AOmXn, where X = fluorine (F), chlorine (Cl), bromine (Br), and/or iodine (I). The element A may be a main group element, a transition element or an actinide. The term oxohalide, or oxyhalide, may also refer to minerals and other crystalline substances with the same overall chemical formula, but having an ionic structure.

References

  1. 1 2 3 IUPAC , Compendium of Chemical Terminology , 2nd ed. (the "Gold Book") (1997). Online corrected version: (2006–) " Halonium ions ". doi : 10.1351/goldbook.H02728
  2. ↑ Peterson, Paul E. (1971-12-01). "Cyclic halonium ions with five-membered rings". Accounts of Chemical Research. 4 (12): 407–413. doi:10.1021/ar50048a003. ISSN   0001-4842.
  3. ↑ Sadek, Omar; Perrin, David M.; Gras, Emmanuel (2019-06-01). "Unsymmetrical diaryliodonium phenyltrifluoroborate salts: Synthesis, structure and fluorination". Journal of Fluorine Chemistry. 222–223: 68–74. doi:10.1016/j.jfluchem.2019.04.004. ISSN   0022-1139. S2CID   132289845.
  4. ↑ Bruice, Paula Yurkanis (2014). Organic Chemistry (7th ed.). Pearson Education. ISBN   978-0-321-80322-1.
  5. ↑ Roberts, Irving; Kimball, George E. (1937). "The Halogenation of Ethylenes". J. Am. Chem. Soc. 59 (5): 947. doi:10.1021/ja01284a507.
  6. ↑ Olah, George A.; DeMember, John R. (1970). "Friedel-Crafts chemistry. V. Isolation, carbon-13 nuclear magnetic resonance, and laser Raman spectroscopic study of dimethylhalonium fluoroantimonates". J. Am. Chem. Soc. 92 (3): 718. doi:10.1021/ja00706a058.
  7. ↑ Pitts, Cody Ross; Holl, Maxwell Gargiulo; Lectka, Thomas (2018). "Spectroscopic Characterization of a [C–F–C]+ fluoronium ion in solution". Angew. Chem. 130 (7). doi: 10.1002/ange.201712021 .
  8. ↑ Mori, T.; Rathore, R. (1998). "X-Ray structure of bridged 2,2′-bi(adamant-2-ylidene) chloronium cation and comparison of its reactivity with a singly bonded chloroarenium cation". ChemComm (8): 927–928. doi:10.1039/a709063c.
  9. ↑ Brown, R. S.; Nagorski, R. W.; Bennet, A. J.; McClung, R. E. D.; Aarts, G. H. M.; Klobukowski, M.; McDonald, R.; Santarsiero, B. D. (March 1994). "Stable Bromonium and Iodonium Ions of the Hindered Olefins Adamantylideneadamantane and Bicyclo[3.3.1]nonylidenebicyclo[3.3.1]nonane. X-Ray Structure, Transfer of Positive Halogens to Acceptor Olefins, and ab Initio Studies". J. Am. Chem. Soc. 116 (6): 2448–2456. doi:10.1021/ja00085a027.
  10. ↑ Schneider, Tobias F.; Werz, Daniel B. (2010). "The Quest for Tetracoordinated Halonium Ions: A Theoretical Investigation". Org. Lett. 12 (21): 4844–4847. doi:10.1021/ol102059b. PMID   20923174.
This page is based on this Wikipedia article
Text is available under the CC BY-SA 4.0 license; additional terms may apply.
Images, videos and audio are available under their respective licenses.