Redistribution (chemistry)

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In chemistry, redistribution usually refers to the exchange of anionic ligands bonded to metal and metalloid centers. The conversion does not involve redox, in contrast to disproportionation 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

Redistribution reactions are exhibited by methylboranes. Thus monomethyldiborane rapidly converts at room temperature to diborane and trimethylborane: [1]

6 MeB2H5 → 5 B2H6 + 2 Me3B

Useful redistribution reactions are found in organoaluminium, organoboron, and organosilicon chemistry. [2] [3]

BCl3 + 2 B(C2H5)3 → 3 BCl(C2H5)2

In another example, tetramethylsilane 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:

SiMe4 + SiCl4 → 2 SiMe2Cl2

In organotin chemistry, the mixed alkyl tin chlorides are produced by redistribution, a reaction called the Kocheshkov comproportionation: [4]

3 SnBu4 + SnCl4 → 4 SnBu3Cl

Many metal halides undergo redistribution reactions, usually to afford nearly statistical mixtures of products. For example, titanium tetrachloride and titanium tetrabromide redistribute their halide ligands, one of many reactions in this conversion is shown: [5]

TiCl4 + TiBr4 → 2 TiBr2Cl2

Related Research Articles

A Ziegler–Natta catalyst, named after Karl Ziegler and Giulio Natta, is a catalyst used in the synthesis of polymers of 1-alkenes (alpha-olefins). Two broad classes of Ziegler–Natta catalysts are employed, distinguished by their solubility:

<span class="mw-page-title-main">Titanium tetrachloride</span> Inorganic chemical compound

Titanium tetrachloride is the inorganic compound with the formula TiCl4. It is an important intermediate in the production of titanium metal and the pigment titanium dioxide. TiCl4 is a volatile liquid. Upon contact with humid air, it forms thick clouds of titanium dioxide and hydrochloric acid, a reaction that was formerly exploited for use in smoke machines. It is sometimes referred to as “tickle” or “tickle 4”, as a phonetic representation of the symbols of its molecular formula.

Tin(IV) chloride, also known as tin tetrachloride or stannic chloride, is an inorganic compound with the formula SnCl4. It is a colorless hygroscopic liquid, which fumes on contact with air. It is used as a precursor to other tin compounds. It was first discovered by Andreas Libavius (1550–1616) and was known as spiritus fumans libavii.

The Kroll process is a pyrometallurgical industrial process used to produce metallic titanium from titanium tetrachloride. The Kroll process replaced the Hunter process for almost all commercial production.

<span class="mw-page-title-main">Organotin chemistry</span> Branch of organic chemistry

Organotin chemistry is the scientific study of the synthesis and properties of organotin compounds or stannanes, which are organometallic compounds containing tin–carbon bonds. The first organotin compound was diethyltin diiodide, discovered by Edward Frankland in 1849. The area grew rapidly in the 1900s, especially after the discovery of the Grignard reagents, which are useful for producing Sn–C bonds. The area remains rich with many applications in industry and continuing activity in the research laboratory.

<span class="mw-page-title-main">Hafnium tetrachloride</span> Chemical compound

Hafnium(IV) chloride is the inorganic compound with the formula HfCl4. This colourless solid is the precursor to most hafnium organometallic compounds. It has a variety of highly specialized applications, mainly in materials science and as a catalyst.

<span class="mw-page-title-main">McMurry reaction</span>

The McMurry reaction is an organic reaction in which two ketone or aldehyde groups are coupled to form an alkene using a titanium chloride compound such as titanium(III) chloride and a reducing agent. The reaction is named after its co-discoverer, John E. McMurry. The McMurry reaction originally involved the use of a mixture TiCl3 and LiAlH4, which produces the active reagents. Related species have been developed involving the combination of TiCl3 or TiCl4 with various other reducing agents, including potassium, zinc, and magnesium. This reaction is related to the Pinacol coupling reaction which also proceeds by reductive coupling of carbonyl compounds.

<span class="mw-page-title-main">Zirconium(IV) chloride</span> Chemical compound

Zirconium(IV) chloride, also known as zirconium tetrachloride, is an inorganic compound frequently used as a precursor to other compounds of zirconium. This white high-melting solid hydrolyzes rapidly in humid air.

Titanium(III) chloride is the inorganic compound with the formula TiCl3. At least four distinct species have this formula; additionally hydrated derivatives are known. TiCl3 is one of the most common halides of titanium and is an important catalyst for the manufacture of polyolefins.

Vanadium tetrachloride is the inorganic compound with the formula VCl4. This reddish-brown liquid serves as a useful reagent for the preparation of other vanadium compounds.

<span class="mw-page-title-main">Organotitanium chemistry</span>

Organotitanium chemistry is the science of organotitanium compounds describing their physical properties, synthesis, and reactions. Organotitanium compounds in organometallic chemistry contain carbon-titanium chemical bonds. They are reagents in organic chemistry and are involved in major industrial processes.

<span class="mw-page-title-main">Mukaiyama aldol addition</span> Organic reaction between a silyl enol ether and an aldehyde or formate

In organic chemistry, the Mukaiyama aldol addition is an organic reaction and a type of aldol reaction between a silyl enol ether and an aldehyde or formate. The reaction was discovered by Teruaki Mukaiyama (1927–2018) in 1973. His choice of reactants allows for a crossed aldol reaction between an aldehyde and a ketone, or a different aldehyde without self-condensation of the aldehyde. For this reason the reaction is used extensively in organic synthesis.

<span class="mw-page-title-main">Trimethyltin chloride</span> Chemical compound

Trimethyltin chloride is an organotin compound with the formula (CH3)3SnCl. It is a white solid that is highly toxic and malodorous. It is susceptible to hydrolysis.

The chloride process is used to separate titanium from its ores. The goal of the process is to win high purity titanium dioxide from ores such as ilmenite (FeTiO3) and rutile (TiO2). The strategy exploits the volatility of TiCl4, which is readily purified and converted to the dioxide. Millions of tons of TiO2 are produced annually by this process, mainly for use as white pigments. The chloride process has largely displaced the older sulfate process, which relies on hot sulfuric acid to extract iron and other impurities from ores..

<span class="mw-page-title-main">Tetramethyltin</span> Chemical compound

Tetramethyltin is an organometallic compound with the formula (CH3)4Sn. This liquid, one of the simplest organotin compounds, is useful for transition-metal mediated conversion of acid chlorides to methyl ketones and aryl halides to aryl methyl ketones. It is volatile and toxic, so care should be taken when using it in the laboratory.

<span class="mw-page-title-main">Silicon tetrabromide</span> Chemical compound

Silicon tetrabromide, also known as tetrabromosilane, is the inorganic compound with the formula SiBr4. This colorless liquid has a suffocating odor due to its tendency to hydrolyze with release of hydrogen bromide. The general properties of silicon tetrabromide closely resemble those of the more commonly used silicon tetrachloride.

In organometallic chemistry, bent metallocenes are a subset of metallocenes. In bent metallocenes, the ring systems coordinated to the metal are not parallel, but are tilted at an angle. A common example of a bent metallocene is Cp2TiCl2. Several reagents and much research is based on bent metallocenes.

<span class="mw-page-title-main">Metal halides</span>

Metal halides are compounds between metals and halogens. Some, such as sodium chloride are ionic, while others are covalently bonded. A few metal halides are discrete molecules, such as uranium hexafluoride, but most adopt polymeric structures, such as palladium chloride.

The +4 oxidation state dominates titanium chemistry, but compounds in the +3 oxidation state are also numerous. Commonly, titanium adopts an octahedral coordination geometry in its complexes, but tetrahedral TiCl4 is a notable exception. Because of its high oxidation state, titanium(IV) compounds exhibit a high degree of covalent bonding.

Hafnium compounds are compounds containing the element hafnium (Hf). Due to the lanthanide contraction, the ionic radius of hafnium(IV) (0.78 ångström) is almost the same as that of zirconium(IV) (0.79 angstroms). Consequently, compounds of hafnium(IV) and zirconium(IV) have very similar chemical and physical properties. Hafnium and zirconium tend to occur together in nature and the similarity of their ionic radii makes their chemical separation rather difficult. Hafnium tends to form inorganic compounds in the oxidation state of +4. Halogens react with it to form hafnium tetrahalides. At higher temperatures, hafnium reacts with oxygen, nitrogen, carbon, boron, sulfur, and silicon. Some compounds of hafnium in lower oxidation states are known.

References

  1. Bell, R. P.; Emeléus, H. J. (1948). "The Boron Hydrides and Related Compounds". Quarterly Reviews, Chemical Society. 2 (2): 132. doi:10.1039/QR9480200132.. The authors refer to redistributions as "disproportionations".
  2. Greenwood, N. N.; & Earnshaw, A. (1997). Chemistry of the Elements (2nd Edn.), Oxford:Butterworth-Heinemann. ISBN   0-7506-3365-4.
  3. Many mixed organo-chloro derivatives of many metalloids are produced in this manner. In one example, Köster, R.; Binger, P. (2007). Chlorodiethylborane and Chlorodiphenylborane" 2007;. Inorganic Syntheses. Vol. 15. pp. 149–153. doi:10.1002/9780470132463.ch33. ISBN   9780470132463.
  4. G. G. Graf (2005). "Tin, Tin Alloys, and Tin Compounds". Ullmann's Encyclopedia of Industrial Chemistry. Weinheim: Wiley-VCH. doi:10.1002/14356007.a27_049. ISBN   978-3527306732.
  5. S. P. Webb and M. S. Gordon (1999). "Intermolecular Self-Interactions of the Titanium Tetrahalides TiX4 (X = F, Cl, Br)". J. Am. Chem. Soc. 121 (11): 2552–2560. doi:10.1021/ja983339i.