Iodine compounds
X | XX | HX | BX3 | AlX3 | CX4 |
---|---|---|---|---|---|
F | 159 | 574 | 645 | 582 | 456 |
Cl | 243 | 428 | 444 | 427 | 327 |
Br | 193 | 363 | 368 | 360 | 272 |
I | 151 | 294 | 272 | 285 | 239 |
Iodine compounds are compounds containing the element
Charge-transfer complexes
The iodine molecule, I2, dissolves in CCl4 and aliphatic hydrocarbons to give bright violet solutions. In these solvents the absorption band maximum occurs in the 520 – 540 nm region and is assigned to a π* to σ* transition. When I2 reacts with Lewis bases in these solvents a blue shift in I2 peak is seen and the new peak (230 – 330 nm) arises that is due to the formation of adducts, which are referred to as charge-transfer complexes.[3]
Hydrogen iodide
The simplest compound of iodine is
- 2 I2 + N2H4 4 HI + N2
At room temperature, it is a colourless gas, like all of the hydrogen halides except
Aqueous hydrogen iodide is known as hydroiodic acid, which is a strong acid. Hydrogen iodide is exceptionally soluble in water: one litre of water will dissolve 425 litres of hydrogen iodide, and the saturated solution has only four water molecules per molecule of hydrogen iodide.[6] Commercial so-called "concentrated" hydroiodic acid usually contains 48–57% HI by mass; the solution forms an azeotrope with boiling point 126.7 °C at 56.7 g HI per 100 g solution. Hence hydroiodic acid cannot be concentrated past this point by evaporation of water.[5]
Unlike
2 ions – the latter, in any case, are much less stable than the bifluoride ions (HF−
2) due to the very weak hydrogen bonding between hydrogen and iodine, though its salts with very large and weakly polarising cations such as Cs+ and NR+
4 (R = Me, Et, Bun) may still be isolated. Anhydrous hydrogen iodide is a poor solvent, able to dissolve only small molecular compounds such as nitrosyl chloride and phenol, or salts with very low lattice energies such as tetraalkylammonium halides.[5]
Other binary iodides
Nearly all elements in the periodic table form binary iodides. The exceptions are decidedly in the minority and stem in each case from one of three causes: extreme inertness and reluctance to participate in chemical reactions (the noble gases); extreme nuclear instability hampering chemical investigation before decay and transmutation (many of the heaviest elements beyond bismuth); and having an electronegativity higher than iodine's (oxygen, nitrogen, and the first three halogens), so that the resultant binary compounds are formally not iodides but rather oxides, nitrides, or halides of iodine. (Nonetheless, nitrogen triiodide is named as an iodide as it is analogous to the other nitrogen trihalides.)[7]
Given the large size of the iodide anion and iodine's weak oxidising power, high oxidation states are difficult to achieve in binary iodides, the maximum known being in the pentaiodides of
Lower iodides may be produced either through thermal decomposition or disproportionation, or by reducing the higher iodide with hydrogen or a metal, for example:[7]
Most metal iodides with the metal in low oxidation states (+1 to +3) are ionic. Nonmetals tend to form covalent molecular iodides, as do metals in high oxidation states from +3 and above. Both ionic and covalent iodides are known for metals in oxidation state +3 (e.g.
Iodine halides
The halogens form many binary,
2 and the dark brown or purplish black compounds of I2Cl+. Apart from these, some pseudohalides are also known, such as cyanogen iodide (ICN), iodine thiocyanate (ISCN), and iodine azide (IN3).[8]
2X+
and IX−
2 anions (X = Cl, Br); thus they are significant conductors of electricity and can be used as ionising solvents.[8]
Iodine trifluoride (IF3) is an unstable yellow solid that decomposes above −28 °C. It is thus little-known. It is difficult to produce because fluorine gas would tend to oxidise iodine all the way to the pentafluoride; reaction at low temperature with xenon difluoride is necessary. Iodine trichloride, which exists in the solid state as the planar dimer I2Cl6, is a bright yellow solid, synthesised by reacting iodine with liquid chlorine at −80 °C; caution is necessary during purification because it easily dissociates to iodine monochloride and chlorine and hence can act as a strong chlorinating agent. Liquid iodine trichloride conducts electricity, possibly indicating dissociation to ICl+
2 and ICl−
4 ions.[9]
Iodine pentafluoride (IF5), a colourless, volatile liquid, is the most thermodynamically stable iodine fluoride, and can be made by reacting iodine with fluorine gas at room temperature. It is a fluorinating agent, but is mild enough to store in glass apparatus. Again, slight electrical conductivity is present in the liquid state because of dissociation to IF+
4 and IF−
6. The pentagonal bipyramidal iodine heptafluoride (IF7) is an extremely powerful fluorinating agent, behind only chlorine trifluoride, chlorine pentafluoride, and bromine pentafluoride among the interhalogens: it reacts with almost all the elements even at low temperatures, fluorinates Pyrex glass to form iodine(VII) oxyfluoride (IOF5), and sets carbon monoxide on fire.[10]
Iodine oxides and oxoacids
E°(couple) | a(H+) = 1 (acid) |
E°(couple) | a(OH−) = 1 (base) |
---|---|---|---|
I2/I− | +0.535 | I2/I− | +0.535 |
HOI/I− | +0.987 | IO−/I− | +0.48 |
IO− 3/I− |
+0.26 | ||
HOI/I2 | +1.439 | IO−/I2 | +0.42 |
IO− 3/I2 |
+1.195 | ||
IO− 3/HOI |
+1.134 | IO− 3/IO− |
+0.15 |
IO− 4/IO− 3 |
+1.653 | ||
H5IO6/IO− 3 |
+1.601 | H 3IO2− 6/IO− 3 |
+0.65 |
More important are the four oxoacids:
I2 + H2O ⇌ HIO + H+ + I− Kac = 2.0 × 10−13 mol2 l−2 I2 + 2 OH− ⇌ IO− + H2O + I− Kalk = 30 mol−1 l
Hypoiodous acid is unstable to disproportionation. The hypoiodite ions thus formed disproportionate immediately to give iodide and iodate:[13]
3 IO− ⇌ 2 I− + IO−
3K = 1020
Iodous acid and iodite are even less stable and exist only as a fleeting intermediate in the oxidation of iodide to iodate, if at all.[13] Iodates are by far the most important of these compounds, which can be made by oxidising alkali metal iodides with oxygen at 600 °C and high pressure, or by oxidising iodine with chlorates. Unlike chlorates, which disproportionate very slowly to form chloride and perchlorate, iodates are stable to disproportionation in both acidic and alkaline solutions. From these, salts of most metals can be obtained. Iodic acid is most easily made by oxidation of an aqueous iodine suspension by electrolysis or fuming nitric acid. Iodate has the weakest oxidising power of the halates, but reacts the quickest.[14]
Many periodates are known, including not only the expected tetrahedral IO−
4, but also square-pyramidal IO3−
5, octahedral orthoperiodate IO5−
6, [IO3(OH)3]2−, [I2O8(OH2)]4−, and I
2O4−
9. They are usually made by oxidising alkaline
- IO−
3 + 6 OH− → IO5−
6 + 3 H2O + 2 e− - IO−
3 + 6 OH− + Cl2 → IO5−
6 + 2 Cl− + 3 H2O
They are thermodymically and kinetically powerful oxidising agents, quickly oxidising Mn2+ to
6 cation, isoelectronic to Te(OH)6 and Sb(OH)−
6, and giving salts with bisulfate and sulfate.[11]
Polyiodine compounds
When iodine dissolves in strong acids, such as fuming sulfuric acid, a bright blue
2 cations is formed. A solid salt of the diiodine cation may be obtained by oxidising iodine with antimony pentafluoride:[11]
- 2 I2 + 5 SbF5 2 I2Sb2F11 + SbF3
The salt I2Sb2F11 is dark blue, and the blue tantalum analogue I2Ta2F11 is also known. Whereas the I–I bond length in I2 is 267 pm, that in I+
2 is only 256 pm as the missing electron in the latter has been removed from an antibonding orbital, making the bond stronger and hence shorter. In fluorosulfuric acid solution, deep-blue I+
2 reversibly dimerises below −60 °C, forming red rectangular diamagnetic I2+
4. Other polyiodine cations are not as well-characterised, including bent dark-brown or black I+
3 and centrosymmetric C2h green or black I+
5, known in the AsF−
6 and AlCl−
4 salts among others.[11][16]
The only important polyiodide anion in aqueous solution is linear triiodide, I−
3. Its formation explains why the solubility of iodine in water may be increased by the addition of potassium iodide solution:[11]
- I2 + I− ⇌ I−
3 (Keq = ~700 at 20 °C)
Many other polyiodides may be found when solutions containing iodine and iodide crystallise, such as I−
5, I−
9, I2−
4, and I2−
8, whose salts with large, weakly polarising cations such as Cs+ may be isolated.[11][17]
Organoiodine compounds
Organoiodine compounds have been fundamental in the development of organic synthesis, such as in the Hofmann elimination of amines,[18] the Williamson ether synthesis,[19] the Wurtz coupling reaction,[20] and in Grignard reagents.[21]
The
Some drawbacks of using organoiodine compounds as compared to organochlorine or organobromine compounds is the greater expense and toxicity of the iodine derivatives, since iodine is expensive and organoiodine compounds are stronger alkylating agents.[27] For example, iodoacetamide and iodoacetic acid denature proteins by irreversibly alkylating cysteine residues and preventing the reformation of disulfide linkages.[28]
Halogen exchange to produce iodoalkanes by the
See also
References
- ^ a b Greenwood and Earnshaw, pp. 804-9
- ^ Greenwood and Earnshaw, pp. 800–4
- ^ Greenwood and Earnshaw, pp. 806-7
- ^ Greenwood and Earnshaw, pp. 809–12
- ^ a b c Greenwood and Earnshaw, pp. 812–9
- ISBN 0-12-352651-5.
- ^ a b c d Greenwood and Earnshaw, pp. 821–4
- ^ a b c d Greenwood and Earnshaw, pp. 824–8
- ^ Greenwood and Earnshaw, pp. 828–831
- ^ Greenwood and Earnshaw, pp. 832–835
- ^ ISBN 978-0-471-18602-1.
- ^ Greenwood and Earnshaw, pp. 851–3
- ^ a b c d Greenwood and Earnshaw, pp. 853–9
- ^ Greenwood and Earnshaw, pp. 863–4
- ^ a b Greenwood and Earnshaw, pp. 872–5
- ^ Greenwood and Earnshaw, pp. 842–4
- ^ Greenwood and Earnshaw, pp. 835–9
- .
- )
- .
- ^ Grignard V (1900). "Sur quelques nouvelles combinaisons organométaliques du magnésium et leur application à des synthèses d'alcools et d'hydrocabures". Compt. Rend. 130: 1322–25.
- ISBN 978-3527306732.
- PMID 12693923. Archived from the original(PDF) on 6 February 2009. Retrieved 25 October 2017.
- ^ Boeckman Jr RK, Shao P, Mullins JJ (2000). "Dess–Martin periodinane: 1,1,1-Triacetoxy-1,1-dihydro-1,2-benziodoxol-3(1H)-one" (PDF). Organic Syntheses. 77: 141; Collected Volumes, vol. 10, p. 696.
- PMID 11671809.
- ^ ISBN 978-0-471-72091-1
- ^ "Safety data for iodomethane". Oxford University.
- PMID 488108.
- S2CID 41232118.
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