Halogen pentafluorides

Fig. 11. Variation in i F shielding down the group of the central atom in hexafluoride ions and molecules and in halogen pentafluorides. Explanation of symbols ...

The halogen pentafluorides and the [XeF5]+ cation have a square pyramidal configuration and any weak secondary bonds are found below the base of the pyramid and situated to avoid the axial, lone pair position. These contacts are much more significant for the xenon compounds than for the interhalogens, where they are so weak as to be virtually indistinguishable from normal intermolecular contacts, as seen in the structure of IF5.40... 

Weak acidity of CIF3 explains the fact that there are no reactions of the solvent with LiF and NaF, whereas a strong acid BrFj reacts appreciably with the latter fluoride. As for halogen pentafluorides, their acidities increase in the sequence ClFj-BrFj-IFj. This conclusion can be made also on the basis of stability of corresponding ammonium salts of NH4XF5 composition. 

Sihcon and boron bum ia fluorine forming siUcon tetrafluoride [7783-61-17, SiF, and boron trifluoride [7637-07-2] respectively. Selenium and tellurium form hexafluorides, whereas phosphoms forms tri- or pentafluorides. Fluorine reacts with the other halogens to form eight interhalogen compounds (see Fluorine compounds, inorganic-halogens). 

Fluorine reacts with the halogens and antimony to produce several compounds of commercial importance antimony pentafluoride [7783-70-2J, bromine trifluoride [7787-71 chlorine trifluoride [7790-91 -2J, and iodine pentafluoride [7783-66-6J. Chlorine trifluoride is used in the processing of UF (see Uraniumand uranium compounds). Bromine trifluoride is used in chemical cutting by the oil well industry (see Petroleum). Antimony and iodine pentafluorides are used as selective fluorinating agents to produce fluorochemical intermediates (see Fluorine compounds, inorganic). 

The halogen fluorides are binary compounds of bromine, chlorine, and iodine with fluorine. Of the eight known compounds, only bromine trifluoride, chlorine trifluoride, and iodine pentafluoride have been of commercial importance. Properties and appHcations have been reviewed (1 7) as have the reactions with organic compounds (8). Reviews covering the methods of preparation, properties, and analytical chemistry of the halogen fluorides are also available (9). 

The halogen fluorides are best prepared by the reaction of fluorine with the corresponding halogen. These compounds are powerful oxidising agents chlorine trifluoride approaches the reactivity of fluorine. In descending order of reactivity the halogen fluorides are chlorine pentafluoride [13637-63-3] 1 5 chlorine trifluoride [7790-91-2] 3 bromine pentafluoride [7789-30-2], BrF iodine heptafluoride [16921 -96-3], chlorine... 

Liquid Halogen Fluorides as Reaction Media. Bromine trifluoride and iodine pentafluoride are highly dimerized and behave as ionizing... 

The pentahalides of phosphorus, PX, in the gas phase exhibit varying tendencies to dissociate into trihaUde and halogen. InstabiUty increases with increasing ionic radius of the halogen. The pentafluoride appears to be thermally stable. Dissociation of the pentachloride, a few percent at 100°C and 101.3 kPa (1 atm), is essentially completed at 300°C (36). The pentabromide is partially dissociated in the Hquid state and totally dissociated above ca 35°C (39). Pentaiodide does not exist. The molecules of PF and PCl in the vapor phase are trigonal bipyramids. In the crystalline state, both pentachloride and pentabromide have ionic stmctures, ie, [PClJ IPClg] and [PBr4]" PBrJ , respectively. The PX" 4 cations are tetrahedral and the PX anion is octahedral (36,37). 

Additions of halogen fluorides to the more electrophilic perfluonnated olefins generally require different conditions Reactions of iodine fluoride, generated in situ from iodine and iodine pentafluoride [62 102 103, /05] or iodine, hydrogen fluoride, and parapeiiodic aud [104], with fluormated olefins (equations 8-10) are especially well studied because the perfluoroalkyl iodide products are useful precursors of surfactants and other fluorochemicals Somewhat higher temperatures are required compared with reactions with hydrocarbon olefins Additions of bromine fluoride, from bromine and bromine trifluonde, to perfluonnated olefins are also known [lOti]... 

Addition of carbon and fluorine can also be initiated by elettraphilic attack on a/luorinated otefin under strongly acidic conditions [250, 251, 252,253 254 255] Best known are fluoroalkylations ot tetrafluoroethylene by tertiary or highly halogenated allylic or benzylic cations in the presence of antimony pentafluoride (equation 53)... 

Vinyl and phenyl mfluoromethyl groups are reactive in the presence of aluminum chloride [10] Replacement of fluorine by chlorine often occurs Polyfluori-nated trifluoromethylbenzenes form reactive a,a-difluorobenzyl cations in antimony pentafluoride [11] 1 Phenylperfluoropropene cyclizes in aluminum chloride to afford 1,1,3-trichloro 2 fluoroindene [10] (equation 10) The reaction IS hypothesized to proceed via an allylic carbocation, whose fluoride atoms undergo halogen exchange... 

Ammonium perchlorate Carbon Bromine pentafluoride Acids, etc. Bromine trifluoride Halogens, etc. Chlorine trifluoride Metals, etc. MRH 6.19/85... 

Halogens, or Interhalogens See Bromine trifluoride Halogens Bromine pentafluoride Acids, etc. 

Bromine pentafluoride is prepared by fluorination of bromine at 200°C. The reaction is carried out in an iron or copper vessel. The halogens are diluted in nitrogen. 

Carbon monoxide is a highly flammable and poisonous gas. Its flammable limits in air are 12.5 to 74.2% by volume, and the autoignition temperature 700°C. It explodes when exposed to flame. Reactions with interhalogen compounds, such as, bromine pentafluoride or halogen oxides can cause explosion. It forms explosive products with sodium or potassium that are sensitive to heat and shock. 

Fluorine also reacts with other halogens, forming interhalogen compounds. While with bromine and iodine it reacts vigorously at ordinary temperatures, with chlorine the reaction occurs at 200°C. Such interhalogen products with these halogens include iodine heptafluoride, bromine trifluoride, bromine pentafluoride, and chlorine trifluoride. Metalloid elements, such as arsenic, silicon, selenium, and boron also inflame in a stream of fluorine, forming fluorides. 

Iodine pentafluoride similar to other halogen fluorides exhibits amphoteric behavior i.e., with strong Lewis acids, such as SbFs, it can form cation, IF4 ... 

Halogens react with the metal at elevated temperatures. Fluorine reacts with ruthenium at 300°C forming colorless vapors of pentafluoride, RuFs, which at ordinary temperatures converts to a green solid. Chlorine combines with the metal at 450°C to form black trichloride, RuCF, which is insoluble in water. Ru metal at ambient temperature is attacked by chlorine water, bromine water, or alcoholic solution of iodine. 

Moissan reasoned that if he were trying to liberate chlorine he would not choose a stable solid like sodium chloride, but a volatile compound like hydrochloric acid or phosphorus pentachloride. His preliminary experiments with silicon fluoride convinced him that this was a very stable compound, and that, if he should ever succeed in isolating fluorine, it would unite with silicon with incandescence, and that therefore he might use silicon in testing for the new halogen. After many unsuccessful attempts to electrolyze phosphorus trifluoride and arsenic trifluoride, and after four interruptions caused by serious poisoning, he finally obtained powdered arsenic at the cathode and some gas bubbles at the anode. However, before these fluorine bubbles could reach the surface, they were absorbed by the arsenic trifluoride to form pentafluoride (18, 23). 

Among the oxidative procedures for preparing azo compounds are oxidation of aromatic amines with activated manganese dioxide oxidation of fluorinated aromatic amines with sodium hypochlorite oxidation of aromatic amines with peracids in the presence of cupric ions oxidation of hindered aliphatic amines with iodine pentafluoride oxidation of both aromatic and aliphatic hydrazine derivatives with a variety of reagents such as hydrogen peroxide, halogens or hypochlorites, mercuric oxide, A-bromosuccinimide, nitric acid, and oxides of nitrogen. 

---