Chlorine monofluoride

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Chlorine monofluoride is a volatile interhalogen compound with the chemical formula ClF. It is a colourless gas at room temperature and is stable even at high temperatures. When cooled to −100 °C, ClF condenses as a pale yellow liquid. Many of its properties are intermediate between its parent halogens, Cl2 and F2.

Geometry

The molecular structure in the gas phase was determined by microwave spectroscopy; the bond length is re = 1.628341(4) Å. The bond length in the crystalline ClF is 1.628(1) Å; the lengthening relative to the free molecule is due to an interaction of the type F-Br···ClMe with a distance of 2.640(1) Å. In its molecular packing it shows very short intermolecular Cl···Cl contacts of 3.070(1) Å between neighboring molecules.

Reactivity

Chlorine monofluoride is a versatile fluorinating agent, converting metals and non-metals to their fluorides and releasing Cl2 in the process. For example, it converts tungsten to tungsten hexafluoride and selenium to selenium tetrafluoride: FCl can also chlorofluorinate compounds, either by addition across a multiple bond or via oxidation. For example, it adds fluorine and chlorine to the carbon of carbon monoxide, yielding carbonyl chloride fluoride:

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