Bromine compounds

Bromine compounds are compounds containing the element bromine (Br). These compounds usually form the 1, +1, +3 and +5 oxidation states. Bromine is intermediate in reactivity between chlorine and iodine, and is one of the most reactive elements. Bond energies to bromine tend to be lower than those to chlorine but higher than those to iodine, and bromine is a weaker oxidising agent than chlorine but a stronger one than iodine. This can be seen from the standard electrode potentials of the X/X couples (F, +2.866 V; Cl, +1.395 V; Br, +1.087 V; I, +0.615 V; At, approximately +0.3 V). Bromination often leads to higher oxidation states than iodination but lower or equal oxidation states to chlorination. Bromine tends to react with compounds including M–M, M–H, or M–C bonds to form M–Br bonds. {| class="wikitable" style="float:right; margin top:0; margin left:1em; text align:center; font size:10pt; line height:11pt; width:25%;"
|+ style="margin bottom: 5px;" | Halogen bond energies (kJ/mol)
2 P + 6 HO + 3 Br → 6 HBr + 2 HPO
HPO + HO + Br → 2 HBr + HPO

At room temperature, hydrogen bromide is a colourless gas, like all the hydrogen halides apart from hydrogen fluoride, since hydrogen cannot form strong hydrogen bonds to the large and only mildly electronegative bromine atom; however, weak hydrogen bonding is present in solid crystalline hydrogen bromide at low temperatures, similar to the hydrogen fluoride structure, before disorder begins to prevail as the temperature is raised. Unlike hydrogen fluoride, anhydrous liquid hydrogen bromide is difficult to work with as a solvent, because its boiling point is low, it has a small liquid range, its dielectric constant is low and it does not dissociate appreciably into HBr and HBr2 ions – the latter, in any case, are much less stable than the bifluoride ions (HF2 ) due to the very weak hydrogen bonding between hydrogen and bromine, though its salts with very large and weakly polarising cations such as Cs and NR4+ (R = Me, Et, Bu) may still be isolated. Anhydrous hydrogen bromide is a poor solvent, only able to dissolve small molecular compounds such as nitrosyl chloride and phenol, or salts with very low lattice energies such as tetraalkylammonium halides. Bromination of metals with Br tends to yield lower oxidation states than chlorination with Cl when a variety of oxidation states is available. Bromides can be made by reaction of an element or its oxide, hydroxide, or carbonate with hydrobromic acid, and then dehydrated by mildly high temperatures combined with either low pressure or anhydrous hydrogen bromide gas. These methods work best when the bromide product is stable to hydrolysis; otherwise, the possibilities include high temperature oxidative bromination of the element with bromine or hydrogen bromide, high temperature bromination of a metal oxide or other halide by bromine, a volatile metal bromide, carbon tetrabromide, or an organic bromide. For example, niobium(V) oxide reacts with carbon tetrabromide at 370 °C to form niobium(V) bromide. The pale brown bromine monofluoride (BrF) is unstable at room temperature, disproportionating quickly and irreversibly into bromine, bromine trifluoride, and bromine pentafluoride. It thus cannot be obtained pure. It may be synthesised by the direct reaction of the elements, or by the comproportionation of bromine and bromine trifluoride at high temperatures. Bromine pentafluoride (BrF) was first synthesised in 1930. It is produced on a large scale by direct reaction of bromine with excess fluorine at temperatures higher than 150 °C, and on a small scale by the fluorination of potassium bromide at 25 °C. It also reacts violently with water and is a very strong fluorinating agent, although chlorine trifluoride is still stronger.

Although dibromine is a strong oxidising agent with a high first ionisation energy, very strong oxidisers such as peroxydisulfuryl fluoride (SOF) can oxidise it to form the cherry red Br2+ cation. A few other bromine cations are known, namely the brown Br3+ and dark brown Br5+. The tribromide anion, Br3 , has also been characterised; it is analogous to triiodide.

+ Standard reduction potentials for aqueous Br species and may be made from the low temperature decomposition of bromine dioxide in a vacuum. It oxidises iodine to iodine pentoxide and benzene to 1,4 benzoquinone; in alkaline solutions, it gives the hypobromite anion. So called "bromine dioxide", a pale yellow crystalline solid, may be better formulated as bromine perbromate, BrOBrO. It is thermally unstable above −40 °C, violently decomposing to its elements at 0 °C. Dibromine trioxide, syn BrOBrO, is also known; it is the anhydride of hypobromous acid and bromic acid. It is an orange crystalline solid which decomposes above −40 °C; if heated too rapidly, it explodes around 0 °C. A few other unstable radical oxides are also known, as are some poorly characterised oxides, such as dibromine pentoxide, tribromine octoxide, and bromine trioxide. {| Br + HO HOBr + H + Br K = 7.2 × 10 mol l Br + 2 OH OBr + HO + Br K = 2 × 10 mol l

Hypobromous acid is unstable to disproportionation. The hypobromite ions thus formed disproportionate readily to give bromide and bromate: More important are the bromates, which are prepared on a small scale by oxidation of bromide by aqueous hypochlorite, and are strong oxidising agents. Unlike chlorates, which very slowly disproportionate to chloride and perchlorate, the bromate anion is stable to disproportionation in both acidic and aqueous solutions. Bromic acid is a strong acid. Bromides and bromates may comproportionate to bromine as follows:

Like the other carbon–halogen bonds, the C–Br bond is a common functional group that forms part of core organic chemistry. Formally, compounds with this functional group may be considered organic derivatives of the bromide anion. Due to the difference of electronegativity between bromine (2.96) and carbon (2.55), the carbon atom in a C–Br bond is electron deficient and thus electrophilic. The reactivity of organobromine compounds resembles but is intermediate between the reactivity of organochlorine and organoiodine compounds. For many applications, organobromides represent a compromise of reactivity and cost. Organobromides are the most common organohalides in nature, even though the concentration of bromide is only 0.3% of that for chloride in sea water, because of the easy oxidation of bromide to the equivalent of Br, a potent electrophile. The enzyme bromoperoxidase catalyzes this reaction. The oceans are estimated to release 1–2 million tons of bromoform and 56,000 tons of bromomethane annually. An old qualitative test for the presence of the alkene functional group is that alkenes turn brown aqueous bromine solutions colourless, forming a bromohydrin with some of the dibromoalkane also produced. The reaction passes through a short lived strongly electrophilic bromonium intermediate. This is an example of a halogen addition reaction.