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In chemistry, chloryl refers to a triatomic cation with
There are two categories of chloryl compounds. The first category is colorless, and includes
chemical formula
In chemistry, a chemical formula is a way of presenting information about the chemical proportions of atoms that constitute a particular chemical compound or molecule, using chemical element symbols, numbers, and sometimes also other symbol ...
. This species has the same general structure as chlorite () but it is electronically different, with chlorine having a +5 oxidation state
In chemistry, the oxidation state, or oxidation number, is the hypothetical charge of an atom if all of its bonds to different atoms were fully ionic. It describes the degree of oxidation (loss of electrons) of an atom in a chemical compound. C ...
(rather than the +3 of chlorite). This makes it a rare example of a positively charged oxychloride. Chloryl compounds, such as and lO2RuF6], are all highly reactive and react violently with water and most organic compounds.
Structure
The cation isisoelectronic
Isoelectronicity is a phenomenon observed when two or more molecules have the same structure (positions and connectivities among atoms) and the same electronic configurations, but differ by what specific elements are at certain locations in th ...
with , and has a bent structure with a bond angle close to 120°. The Cl–O bond is of bond order 1.5, with its Lewis structure consisting of a double bond
In chemistry, a double bond is a covalent bond between two atoms involving four bonding electrons as opposed to two in a single bond. Double bonds occur most commonly between two carbon atoms, for example in alkenes. Many double bonds exist betwee ...
and a dative bond
In coordination chemistry, a coordinate covalent bond, also known as a dative bond, dipolar bond, or coordinate bond is a kind of two-center, two-electron covalent bond in which the two electrons derive from the same atom. The bonding of metal ...
which does not utilize d-orbitals.
The red color of is caused by electron transitions into an antibonding orbital. The analogous transition in is not in the visible spectrum, so is colorless. The strength of interaction with the counterion affects the energy of this antibonding orbital; thus, in colorless chloryl compounds, strong interactions with the counterion, corresponding with the higher covalent character of the bonding, shift the transition energy out of the visible spectrum.
Compounds
There are two categories of chloryl compounds. The first category is colorless, and includes chloryl fluoride
Chloryl fluoride is the chemical compound with the formula ClO2F. It is commonly encountered as side-product in reactions of chlorine fluorides with oxygen sources. It is the acyl fluoride of chloric acid.
Preparation
ClO2F was first reported by ...
(). These are moderately reactive. Although named as an ionic "chloryl" compound, chloryl fluoride is more a covalent compound than an ionic compound of fluoride and chloryl cation.
The second category features red-colored compounds that are highly reactive. These include chloryl fluorosulfate
In chemistry, chloryl refers to a triatomic cation with chemical formula . This species has the same general structure as chlorite () but it is electronically different, with chlorine having a +5 oxidation state (rather than the +3 of chlorite). ...
, , and dichloryl trisulfate, . These chloryl compounds form red solutions in fluorosulfuric acid, and do contain a red-colored cation which dissociates in solution. In the solid state, the Raman and infrared
Infrared (IR), sometimes called infrared light, is electromagnetic radiation (EMR) with wavelengths longer than those of visible light. It is therefore invisible to the human eye. IR is generally understood to encompass wavelengths from around ...
spectra indicate strong interactions with the counterion. Not all chloryl compounds in the solid state are necessarily ionic. The reaction products of with and are assumed to be molecular adduct
An adduct (from the Latin ''adductus'', "drawn toward" alternatively, a contraction of "addition product") is a product of a direct addition of two or more distinct molecules, resulting in a single reaction product containing all atoms of all co ...
s rather than true salts
In chemistry, a salt is a chemical compound consisting of an ionic assembly of positively charged cations and negatively charged anions, which results in a compound with no net electric charge. A common example is table salt, with positively c ...
.
One notable chloryl compound is dichlorine hexoxide, which exists as an ionic compound more accurately described as ''chloryl perchlorate'', . It is a red fuming liquid under standard conditions.
Chloryl compounds are best prepared by the reaction of with a strong Lewis acid. For example:
: + → lO2AsF6]
Other synthesis routes are also possible, including:
:5 + 3 → 2 lO2AsF6] + + 4
: + 2 → lO2SbF6] + +
Salt metathesis reaction, Metathesis reactions may be carried out with strong Lewis bases. For example, the reaction of the hexafluoroplatinate salt with nitryl fluoride
Nitryl fluoride, NO2F, is a colourless gas and strong oxidizing agent, which is used as a fluorinating agent and has been proposed as an oxidiser in rocket propellants (though never flown).
It is a molecular species, not ionic, consistent with it ...
yields the nitronium salt:
: lO2PtF6] + → O2PtF6] +
References
External links
*{{Commonscatinline, Chloryl cation Chloryl compounds, Cations Oxycations Chlorine oxides