Chloryl fluoride

Chloryl fluoride is the chemical compound with the formula ClO₂F. This compound is a gas boiling at −6 °C. It is commonly encountered as side-product in reactions of chlorine fluorides with oxygen sources.^[1] It is the acyl fluoride of chloric acid.

Chloryl fluoride

Names
Other names Chlorine dioxide fluoride Chlorine(V) fluoride dioxide
Identifiers
CAS Number	13637-83-7 Y
3D model (JSmol)	Interactive image
ChemSpider	123044 N
PubChem CID	139523
CompTox Dashboard (EPA)	DTXSID00159769
InChI InChI=1S/ClFO2/c2-1(3)4 N Key: YVRLYFHVJLYEHM-UHFFFAOYSA-N N InChI=1/ClFO2/c2-1(3)4 Key: YVRLYFHVJLYEHM-UHFFFAOYAO
SMILES FCl(=O)=O
Properties
Chemical formula	ClO2F
Molar mass	86.45 g·mol−1
Appearance	Colorless gas
Density	3.534 g/L
Melting point	−115 °C
Boiling point	−6 °C
Related compounds
Related compounds	Bromyl fluoride Iodyl fluoride Perchloryl fluoride Chloryl trifluoride
Except where otherwise noted, data are given for materials in their standard state (at 25 °C [77 °F], 100 kPa). N verify (what is YN ?) Infobox references

Preparation

ClO₂F was first reported by Schmitz and Schumacher in 1942, who prepared it by the fluorination of ClO₂.^[2] The compound is more conveniently prepared by reaction of sodium chlorate and chlorine trifluoride^[3] and purified by vacuum fractionation, i.e. selectively condensing this species separately from other products.

6 NaClO₃ + 4 ClF₃ → 6 ClO₂F + 2 Cl₂ + 3 O₂ + 6 NaF

Structure

In contrast to O₂F₂, ClO₂F is a pyramidal molecule as predicted by VSEPR. The differing structures reflects the greater tendency of chlorine to exist in positive oxidation states with oxygen and fluorine ligands. The related Cl-O-F compound perchloryl fluoride, ClO₃F, is tetrahedral. The related bromine compound bromyl fluoride (BrO₂F) adopts the same structure as ClO₂F, whereas iodyl fluoride (IO₂F) forms a polymeric substance under standard conditions.^[4]

Precautions

Rocket fuel chemist John Drury Clark reported in his book Ignition! that chloryl fluoride "is indecently reactive, and the hardest to keep of all the CI-O-F compounds, since it apparently dissolves the protective metal fluoride coatings that make the storage of ClF₃ comparatively simple."^[5]