Chlorine oxyfluorides

IV. Appendix Tables of Thermodynamic Properties for Some Chlorine Oxyfluorides. ... 

The subject of chlorine oxyfluorides has been reviewed in 1963 by Schmeisser and Brandle (253) and in 1969 in Gmelin s Handbuch der... 

Fig. 1. Geometries of the chlorine oxyfluoride molecules and their ions compared to those of the corresponding chlorine fluorides. Since the C1+ cation would possess only an electron sextet, it is stabilized by a GIF molecule to form the C12F+...

In addition to a discussion of the individual compounds, a section was added correlating the physical and chemical properties of the chlorine oxyfluorides with their structure. In the Appendix, full tables of thermodynamic properties are given for each compound, where known. 

As can be seen from Fig. 1, the structures of all the chlorine oxyfluoride molecules and ions can be derived from those of the corresponding binary chlorine fluorides (53) by replacing a free chlorine valence electron pair by a doubly bonded oxygen atom without significant rearrangement of the rest of the molecule. 

This rule also holds for the chlorine oxyfluorides as well as for the chlorine fluorides for which it was originally formulated. 

In many respects the chlorine oxyfluorides resemble the chlorine fluorides. For example, they exhibit little or no self-ionization, but are amphoteric. With strong Lewis acids or bases they can form stable adducts. The tendency to form adducts was found (64) not to be so much a function of the relative acidity of the parent chlorine oxyfluoride but rather to depend on the structure of the amphoteric molecule and of that of the anion or the cation formed. The preferred structures are the energetically favored tetrahedron and octahedron. Consequently, a trigonal bipyramidal molecule, such as CIF3O (64), exhibits a pronounced tendency to form either a stable pseudotetrahedral cation or a pseudo-octahedral anion ... 

Similarly, the chemical reactivity of these two chlorine oxyfluorides differs vastly whereas ClFsO is extremely reactive and cannot be handled even in a well-dried glass vacuum system, FCIO3 reacts only slowly with water. 

CHLORINE OXYFLUORIDES TABLE VIII Some Pbopesties of CIF3O... 

Synonyms Chlorine fluoride oxide chlorine oxyfluoride trioxychlorofluoride... 

Chlorine monofluoride oxide, 18 328-330 force field of, 18 329, 330 infrared spectrum of, 18 328, 329 stretching force constants for, 18 330 synthesis of, 18 328 Chlorine nitrate fluorination of, 18 332 preparation of, 5 54 Chlorine oxides, 46 109-110, 158 fluorination of, 18 348 Chlorine oxyfluorides, 18 319-389, see also specific compounds adduct formation, 18 327, 328 amphoteric nature of, 18 327, 328 bond lengths, 18 326 bond strengths, 18 323-327 geometry of, 18 320-323 ligand distribution, 18 323 reactivity of, 18 327, 328 stretching force constants, 18 324-327 Chlorine pentafluoride oxide, 18 345, 346 Chlorine trifluoride, reaction with difluoramine, 33 157... 

Jack M. Miller and Gary L. Wilson The Structures of Elemental Sulfur Beat Meyer Chlorine Oxyfluorides K. O. Christe and C. J. Schack... 

Chloryl fluoride can be prepared in high yield by the action of CIF3 on NaClOs. It is a colorless gas and a powerful oxidizing and fluorinating agent. " " It is the most common chlorine oxyfluoride and is typically encountered in reactions between CIF and oxides or hydroxides. 

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