Bismuth V fluoride

The trihalides closely resemble those of antimony. Bismuth(V) fluoride is known. It is a white solid, and a powerful oxidising agent. 

Bismuth Penta.fIuoride, Bismuth(V) fluoride consists of long white needles that have been shown to have the same stmcture as the body-centered, tetragonal a-polymorph of uranium hexafluoride. The density of the soHd is 5.4 g/mL at 25°C. The soHd consists of infinite chains of trans-bridged BiF polyhedra dimers and trimers are present in the vapor phase (22). Bismuth pentafluoride may be prepared by the fluorination of BiF or... 

Complex fluorides (LiBiF6, and KBiF6) are known1 and they are weaker oxidizing agents than bismuth(V) fluoride itself. If parallels with potassium tetrafluorocobaltate(III) and co-balt(III) fluoride are valid (see Section 25.1.), then they will also be weaker fluorinating agents. 

The rate of oxidation of acetophenoximes with bismuth(V) fluoride in a mixture of hydrogen fluoride and perchloric acid follows first-order kinetics in both the oxime and Bi(V). The reaction is acid catalysed. A bridged outer-sphere mechanism, involving formation of an iminoxy radical, has been suggested.81... 

The oxidations of formaldehyde and ethanolamine " with bismuth(V) fluoride complex in an HCIO4-HF mixture are both first order in each reactant and proceed via a mechanism in which electron transfer from the substrate to the oxidant involves a bridged outer sphere. 

Bismuth pentafluoride is an active fluorinating agent. It reacts explosively with water to form ozone, oxygen difluoride, and a voluminous chocolate-brown precipitate, possibly a hydrated bismuth(V) oxyfluoride. A similar brown precipitate is observed when the white soHd compound bismuth oxytrifluoride [66172-91 -6] BiOF, is hydrolyzed. Upon standing, the chocolate-brown precipitate slowly undergoes reduction to yield a white bismuth(Ill) compound. At room temperature BiF reacts vigorously with iodine or sulfur above 50°C it converts paraffin oil to fluorocarbons at 150°C it fluorinates uranium tetrafluoride to uranium pentafluoride and at 180°C it converts Br2 to bromine trifluoride, BrF, and bromine pentafluoride, BrF, and chlorine to chlorine fluoride, GIF. It apparently does not react with dry oxygen. 

Perhaps the most reactive compound of the group is BiFs- It reacts extremely vigorously with H2O to form O3, OF2 and a voluminous brown precipitate which is probably a hydrated bismuth(V) oxide fluoride. At room temperature BiFs reacts vigorously with iodine or sulfur above 50° it converts paraffin oil to fluorocarbons at 150° it fluorinates UF4 to UF and at 180° it converts Brs to BrFs and BrFs, and CI2 to CIF. 

Bil3 Bismuth(III) iodide, 4 114 2Bi(N03)3-3Mg(N03)2-24H20 Bismuth magnesium nitrate, 2 57 BrF Bromine (I) fluoride, 3 185 BrF3 Bromine(III) fluoride, 3 184 BrF5 Bromine (V) fluoride, 3 185 BrH Hydrobromic acid, 1 151, 152, 155... 

Haloanions of bismuth(V) are limited to the fluorides. Halobismuthates(III) and organohalobis-muthates(III) exhibit a range of structures and among the heavier halogens there is considerable similarity to their antimony (III) analogues. The halobismuthate(III) (not fluorides) structures have been reviewed by Fisher and Norman. ... 

Halides of the type AX6, where A is P, As, Sb, or Bi, and X is F, Cl, Br, or I, may generally be obtained by interaction of the elements. It is also possible to react AX3-type compounds with the corresponding halogen, and this is particularly useful when X = F. The halides SbF6 and BiF6 are made in this way. The compounds SbBr6 (cf. Section II,A,2), Sbl6, and arsenic(V) and bismuth(V) halides other than the fluorides are unknown. 

Other acids in bromine(III) fluoride are the fluorides of boron, gold(III), silicon, germanium, tin(IV), titanium(IV), phosphorus(V), arsenic(V), bismuth(V), vana-dium(V), niobium(V), tantalum(V), ruthenium(V), platinum(V) as well as hydrogen fluoride and sulphur trioxide ... 

Metal Halides. Reacts explosively or violently with the following calcium bromide iron(III) bromide or chloride iron(II) bromide or iodide cobalt(II) chloride silver fluoride all four mercury(II) halides copper(I) chloride, bromide or iodide copper(II) chloride and bromide ammonium tetrachlorocuprate zinc and cadmium chlorides, bromides, and iodides aluminum fluoride, chloride, and bromide thallium bromide tin(II) or (IV) chloride tin(IV) iodide arsenic trichloride and triiodide antimony and bismuth trichlorides, tribromides, and triiodides vanadium(V) chloride chromium(IV) chloride manganese(II) and iron(II) chlorides and nickel chloride, bromide, and iodide.17,22"25... 

Calcium(II), which shows no appreciable complexing, has a distribution coefficient of 147 in 0.5 M perchloric acid and 191 in 0.5 M hydrochloric acid. Strelow. Rethc-meyer, and Bothnia [10] also reported data for nitric and sulfuric acids that showed complexation in some cases. Mercury(II), bismuth(III), cadmium(II), zinc(II), and lead(II) form bromide complexes and are eluted in the order given in 0.1 to 0.6 M hydrobromic acid [11]. Most other metal cations remain on the column. Aluminu-m(III), molybdenum(VI), niobium(V), tin(IV), tantalum(V), uranium(VI), tung-sten(VI), and zirconium(IV) form anionic fluoride complexes and are quickly eluted from a hydrogen-form cation-exchange column with 0.1 to 0.2 M HF [12]. 

Metathesis of triarylbismuth dichloride with a variety of metal salts such as fluoride, azide, cyanide, carboxylates and sulfonates has been used frequently for the synthesis of triarylbismuth(V) compounds of the type Ar Bi Y 2, where Y is the corresponding anionic group (Section 3.1.1). The reaction of triphenyl-bismuth dichloride with mercuric chloride in an alkaline medium leads to triphenylbismuthine, while treatment of triphenylbismuth dicyanide with mercuric oxide results in the formation of triphenylbismuthine oxide (Section... 

---