Ceric ammonium nitrate (CAN) is the

inorganic compound In chemistry, an inorganic compound is typically a chemical compound that lacks carbon–hydrogen bonds, that is, a compound that is not an organic compound. The study of inorganic compounds is a subfield of chemistry known as '' inorganic chemist ...

with the formula . This orange-red, water-soluble

cerium Cerium is a chemical element with the symbol Ce and atomic number 58. Cerium is a soft, ductile, and silvery-white metal that tarnishes when exposed to air. Cerium is the second element in the lanthanide series, and while it often shows the +3 o ...

salt Salt is a mineral composed primarily of sodium chloride (NaCl), a chemical compound belonging to the larger class of salts; salt in the form of a natural crystalline mineral is known as rock salt or halite. Salt is present in vast quantitie ...

is a specialised

oxidizing agent An oxidizing agent (also known as an oxidant, oxidizer, electron recipient, or electron acceptor) is a substance in a redox chemical reaction that gains or "Electron acceptor, accepts"/"receives" an electron from a (called the , , or ). In ot ...

organic synthesis Organic synthesis is a special branch of chemical synthesis and is concerned with the intentional construction of organic compounds. Organic molecules are often more complex than inorganic compounds, and their synthesis has developed into one o ...

and a standard oxidant in quantitative analysis.

Preparation, properties, and structure

The

anion An ion () is an atom or molecule with a net electrical charge. The charge of an electron is considered to be negative by convention and this charge is equal and opposite to the charge of a proton, which is considered to be positive by convent ...

is generated by dissolving in hot and concentrated

nitric acid Nitric acid is the inorganic compound with the formula . It is a highly corrosive mineral acid. The compound is colorless, but older samples tend to be yellow cast due to decomposition into oxides of nitrogen. Most commercially available nitri ...

(). The salt consists of the hexanitratocerate(IV) anion and a pair of

ammonium The ammonium cation is a positively-charged polyatomic ion with the chemical formula or . It is formed by the protonation of ammonia (). Ammonium is also a general name for positively charged or protonated substituted amines and quaternary a ...

cations . The ammonium ions are not involved in the oxidising reactions of this salt. In the anion each nitrate group chelates the cerium atom in a bidentate manner as shown below: The anion has T_h (idealized O_h)

molecular symmetry Molecular symmetry in chemistry describes the symmetry present in molecules and the classification of these molecules according to their symmetry. Molecular symmetry is a fundamental concept in chemistry, as it can be used to predict or explain m ...

. The core defines an

icosahedron In geometry, an icosahedron ( or ) is a polyhedron with 20 faces. The name comes and . The plural can be either "icosahedra" () or "icosahedrons". There are infinitely many non- similar shapes of icosahedra, some of them being more symmetrica ...

. is a strong one-electron

. In terms of its redox potential (E° ~ 1.61 V vs. N.H.E.) it is even stronger oxidizing agent than (E° ~ 1.36 V). Few shelf-stable reagents are stronger oxidants. In the redox process Ce(IV) is converted to Ce(III), a one-electron change, signaled by the fading of the solution color from orange to a pale yellow (providing that the substrate and product are not strongly colored).

Applications in organic chemistry

In organic synthesis, CAN is useful as an oxidant for many functional groups (

alcohols In chemistry, an alcohol is a type of organic compound that carries at least one hydroxyl () functional group bound to a saturated carbon atom. The term ''alcohol'' originally referred to the primary alcohol ethanol (ethyl alcohol), which is ...

phenol Phenol (also called carbolic acid) is an aromatic organic compound with the molecular formula . It is a white crystalline solid that is volatile. The molecule consists of a phenyl group () bonded to a hydroxy group (). Mildly acidic, it req ...

s, and

ether In organic chemistry, ethers are a class of compounds that contain an ether group—an oxygen atom connected to two alkyl or aryl groups. They have the general formula , where R and R′ represent the alkyl or aryl groups. Ethers can again be c ...

s) as well as C–H bonds, especially those that are benzylic.

Alkene In organic chemistry, an alkene is a hydrocarbon containing a carbon–carbon double bond. Alkene is often used as synonym of olefin, that is, any hydrocarbon containing one or more double bonds.H. Stephen Stoker (2015): General, Organic, an ...

s undergo dinitroxylation, although the outcome is solvent-dependent.

Quinone The quinones are a class of organic compounds that are formally "derived from aromatic compounds

uch as benzene or naphthalene Uch ( pa, ; ur, ), frequently referred to as Uch Sharīf ( pa, ; ur, ; ''"Noble Uch"''), is a historic city in the southern part of Pakistan's Punjab province. Uch may have been founded as Alexandria on the Indus, a town founded by Alexand ...

by conversion of an even number of –CH= groups into –C(=O)– groups with any necessary rearrangement of double ...

s are produced from catechols and

hydroquinone Hydroquinone, also known as benzene-1,4-diol or quinol, is an aromatic organic compound that is a type of phenol, a derivative of benzene, having the chemical formula C6H4(OH)2. It has two hydroxyl groups bonded to a benzene ring in a ''para'' ...

s and even

nitroalkane In organic chemistry, nitro compounds are organic compounds that contain one or more nitro functional groups (). The nitro group is one of the most common explosophores (functional group that makes a compound explosive) used globally. The nitr ...

s are oxidized. CAN provides an alternative to the

Nef reaction In organic chemistry, the Nef reaction is an organic reaction describing the acid hydrolysis of a salt of a primary or secondary nitroalkane () to an aldehyde () or a ketone () and nitrous oxide (). The reaction has been the subject of several ...

; for example, for ketomacrolide synthesis where complicating side reactions usually encountered using other reagents. Oxidative halogenation can be promoted by CAN as an ''in situ'' oxidant for benzylic bromination, and the iodination of ketones and

uracil Uracil () (symbol U or Ura) is one of the four nucleobases in the nucleic acid RNA. The others are adenine (A), cytosine (C), and guanine (G). In RNA, uracil binds to adenine via two hydrogen bonds. In DNA, the uracil nucleobase is replaced by ...

derivatives.

For the synthesis of heterocycles

Catalytic amounts of aqueous CAN allow the efficient synthesis of quinoxaline derivatives. Quinoxalines are known for their applications as dyes, organic semiconductors, and DNA cleaving agents. These derivatives are also components in antibiotics such as

echinomycin Echinomycin is a peptide antibiotic. It is a dimer of two peptides creating a cyclic structure. It contains a bicyclic aromatic chromophore that is attached to the dimerized cyclic peptide core and a thioacetal bridge. It intercalates into DNA a ...

and actinomycin. The CAN-catalyzed three-component reaction between

aniline Aniline is an organic compound with the formula C6 H5 NH2. Consisting of a phenyl group attached to an amino group, aniline is the simplest aromatic amine In organic chemistry, an aromatic amine is an organic compound consisting of an aroma ...

s and

alkyl vinyl ether In organic chemistry, an alkyl group is an alkane missing one hydrogen. The term ''alkyl'' is intentionally unspecific to include many possible substitutions. An acyclic alkyl has the general formula of . A cycloalkyl is derived from a cycloalk ...

s provides an efficient entry into 2-methyl-1,2,3,4-tetrahydroquinolines and the corresponding quinolines obtained by their aromatization.

As a deprotection reagent

CAN is traditionally used to release organic ligands from metal carbonyls. In the process, the metal is oxidised, CO is evolved, and the organic ligand is released for further manipulation. For example, with the

Wulff–Dötz reaction The Wulff–Dötz reaction (also known as the Dötz reaction or the benzannulation reaction of the Fischer carbene complexes) is the chemical reaction of an aromatic or vinylic alkoxy pentacarbonyl chromium carbene complex with an alkyne and carbon ...

an alkyne, carbon monoxide, and a chromium

carbene In organic chemistry, a carbene is a molecule containing a neutral carbon atom with a valence of two and two unshared valence electrons. The general formula is or where the R represents substituents or hydrogen atoms. The term "carbene" ma ...

are combined to form a chromium

half-sandwich complex Half sandwich compounds, also known as piano stool complexes, are organometallic complexes that feature a cyclic polyhapto ligand bound to an MLn center, where L is a unidentate ligand. Thousands of such complexes are known. Well-known examples i ...

and the phenol ligand can be isolated by mild CAN oxidation. : CAN is used to cleave ''para''-methoxybenzyl and 3,4-dimethoxybenzyl ethers, which are

protecting group A protecting group or protective group is introduced into a molecule by chemical modification of a functional group to obtain chemoselectivity in a subsequent chemical reaction. It plays an important role in multistep organic synthesis. In many ...

s for alcohols.Boons, Geert-Jan.; Hale, Karl J. (2000). ''Organic Synthesis with Carbohydrates'' (1st ed.) Sheffield, England: Sheffield Academic Press. pp.33Kocienski, Phillip J. (1994). ''Protecting Groups'' Stuttgart, New York Georg Thieme Verlag. pp 8-9, 52-54 Two equivalents of CAN are required for each equivalent of ''para''-methoxybenzyl ether. The alcohol is released, and the ''para''-methoxybenzyl ether converts to ''para''-methoxybenzaldehyde. The balanced equation is as follows: :

Other applications

CAN is also a component of chrome

etchant Etching is a printmaking technique in art. Etching may also refer to: * Etching (microfabrication), a process in producing microelectronics * Glass etching, a glass decoration technique * Chemical milling, or industrial etching * Photochemical ma ...

, a material that is used in the production of photomasks and

liquid crystal display A liquid-crystal display (LCD) is a flat panel display, flat-panel display or other Electro-optic modulator, electronically modulated optical device that uses the light-modulating properties of liquid crystals combined with polarizers. Liqui ...

References

External links

Oxidizing Agents: Cerium Ammonium Nitrate
{{DEFAULTSORT:Ceric Ammonium Nitrate Ammonium compounds Cerium(IV) compounds Nitrates Coordination complexes Oxidizing agents