In chemistry, redistribution usually refers to the exchange of anionic ligands bonded to metal and metalloid centers. The conversion does not involve
redox
Redox (reduction–oxidation, , ) is a type of chemical reaction in which the oxidation states of substrate change. Oxidation is the loss of electrons or an increase in the oxidation state, while reduction is the gain of electrons or a ...
, in contrast to
disproportionation
In chemistry, disproportionation, sometimes called dismutation, is a redox reaction in which one compound of intermediate oxidation state converts to two compounds, one of higher and one of lower oxidation states. More generally, the term can ...
reactions. Some useful redistribution reactions are conducted at higher temperatures; upon cooling the mixture, the product mixture is kinetically frozen and the individual products can be separated. In cases where redistribution is rapid at mild temperatures, the reaction is less useful synthetically but still important mechanistically.
Examples
Rapid redistribution reactions are exhibited by methylboranes. Thus monomethyldiborane rapidly converts at room temperature to
diborane
Diborane(6), generally known as diborane, is the chemical compound with the formula B2H6. It is a toxic, colorless, and pyrophoric gas with a repulsively sweet odor. Diborane is a key boron compound with a variety of applications. It has attracte ...
and
trimethylborane
Trimethylborane (TMB) is a toxic, pyrophoric gas with the formula B(CH3)3 (which can also be written as Me3B, with Me representing methyl).
Properties
As a liquid it is colourless. The strongest line in the infrared spectrum is at 1330 cmâ ...
:
[. The authors refer to redistributions as "disproportionations".]
:6 MeB
2H
5 → 5 B
2H
6 + 2 Me
3B
Useful redistribution reactions are found in
organoaluminium,
organoboron
Organoborane or organoboron compounds are chemical compounds of boron and carbon that are organic derivatives of BH3, for example trialkyl boranes. Organoboron chemistry or organoborane chemistry is the chemistry of these compounds.
Organoboron ...
, and
organosilicon chemistry
Organosilicon compounds are organometallic compounds containing carbon–silicon bonds. Organosilicon chemistry is the corresponding science of their preparation and properties. Most organosilicon compounds are similar to the ordinary organic c ...
.
: BCl
3 + 2 B(C
2H
5)
3 → 3 BCl(C
2H
5)
2
In another example,
tetramethylsilane
Tetramethylsilane (abbreviated as TMS) is the organosilicon compound with the formula Si(CH3)4. It is the simplest tetraorganosilane. Like all silanes, the TMS framework is tetrahedral. TMS is a building block in organometallic chemistry but also ...
is an undesirable product of the industrially important
direct process, but it can be converted (recycled) into more useful products by redistribution with
silicon tetrachloride
Silicon tetrachloride or tetrachlorosilane is the inorganic compound with the formula SiCl4. It is a colourless volatile liquid that fumes in air. It is used to produce high purity silicon and silica for commercial applications.
Preparation
Silic ...
:
: SiMe
4 + SiCl
4 → 2 SiMe
2Cl
2
In
organotin chemistry
Organotin compounds or stannanes are chemical compounds based on tin with hydrocarbon substituents. Organotin chemistry is part of the wider field of organometallic chemistry. The first organotin compound was diethyltin diiodide (), discovered b ...
, the mixed alkyl tin chlorides are produced by redistribution, a reaction called the Kocheshkov comproportionation:
: 3 SnBu
4 + SnCl
4 → 4 SnBu
3Cl
Many metal
halides undergo redistribution reactions, usually to afford nearly statistical mixtures of products. For example,
titanium tetrachloride
Titanium tetrachloride is the inorganic compound with the formula . It is an important intermediate in the production of titanium metal and the pigment titanium dioxide. is a volatile liquid. Upon contact with humid air, it forms thick clouds ...
and
titanium tetrabromide
Titanium tetrabromide is the chemical compound with the formula TiBr4. It is the most volatile transition metal bromide. The properties of TiBr4 are an average of TiCl4 and TiI4. Some key properties of these four-coordinated Ti(IV) species ar ...
redistribute their halide ligands, one of many reactions in this conversion is shown:
: TiCl
4 + TiBr
4 → 2 TiBr
2Cl
2
References
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Chemical reactions
Chemical processes