Chloryl

Structure

The cation is isoelectronic 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 and a dative bond which does not utilize d-orbitals.{{cite journal

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 (). 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, , 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 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 adducts rather than true salts.{{cite book

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:

: + → [ClO2][AsF6]

Other synthesis routes are also possible, including:

:5 + 3 → 2 [ClO2][AsF6] + + 4

: + 2 → [ClO2][SbF6] + +

Metathesis reactions may be carried out with strong Lewis bases. For example, the reaction of the hexafluoroplatinate salt with nitryl fluoride yields the nitronium salt:

:[ClO2][PtF6] + → [NO2][PtF6] +

References

References

1. (1969). "Chloryl cation, {{chem". Inorganic Chemistry.
2. (1991). "Preparation characterization and crystal structure of chloryl hexafluororuthenate(1-). Crystal structure of {{chem". Inorganic Chemistry.
3. (15 December 1969). "Chloryl compounds. Part II. Chloryl hexafluoroarsenate and chloryl fluoride". Canadian Journal of Chemistry.
4. (1986). "Crystal Structure of {{chem". Angewandte Chemie International Edition in English.