Tin(IV) chloride, also known as tin tetrachloride or stannic chloride, is an inorganic compound of tin and chlorine 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.<ref name = "Wiberg&Holleman">Template:Cite book</ref> It was first discovered by Andreas Libavius (1550–1616) and was known as spiritus fumans libavii.
PreparationEdit
It is prepared from reaction of chlorine gas with tin at Template:Convert:
StructureEdit
_chloride_space-filling3D.png){kind=link}
Anhydrous tin(IV) chloride solidifies at −33 °C to give monoclinic crystals with the P21/c space group. It is isostructural with SnBr4. The molecules adopt near-perfect tetrahedral symmetry with average Sn–Cl distances of 227.9(3) pm.<ref>Template:Cite journal</ref>
ReactionsEdit
Tin(IV) chloride is well known as a Lewis acid. Thus it forms hydrates. The pentahydrate SnCl4·5H2O was formerly known as butter of tin. These hydrates consist of cis-[SnCl4(H2O)2] molecules together with varying amounts of water of crystallization. The additional water molecules link together the molecules of [SnCl4(H2O)2] through hydrogen bonds. A pentahydrate has also been crystallized. In cis-Template:Chem2, the Sn-Cl bonds are 238.3 pm.<ref>Template:Cite journal</ref> Although the pentahydrate is the most common hydrate, lower hydrates have also been characterised.<ref>Template:Cite journal</ref>
Aside from water, other Lewis bases form adducts with SnCl4. These include ammonia and organophosphines.
The ammonium salt of [SnCl6]2− is formed from ammonium chloride. It is called "pink salt":<ref name=Ullmann/>
The analogous reaction with hydrochloric acid gives "hexachlorostannic acid".<ref name = "Wiberg&Holleman"/>
Reaction of the tetrachloride with hydrogen fluoride gives tin tetrafluoride:<ref name=Ullmann/>
Tin(IV) chloride undergoes redistribution with tin(IV) bromide as assessed by 119Sn NMR and Raman spectroscopy. Equilibrium is achieved in seconds at room temperature. By contrast, halide exchange for related germanium and especially silicon halides is slower.<ref>Template:Cite journal</ref>
ApplicationsEdit
Precursor to organotin compoundsEdit
Anhydrous tin(IV) chloride is a major precursor in organotin chemistry. Upon treatment with Grignard reagents, tin(IV) chloride gives tetraalkyltin compounds:<ref name = "Greenwood">Template:Greenwood&Earnshaw</ref>
- SnCl4 + 4 RMgCl → SnR4 + 4 MgCl2
Anhydrous tin(IV) chloride reacts with tetraorganotin compounds in redistribution reactions:
- SnCl4 + SnR4 → 2 SnCl2R2
These organotin halides are useful precursors to catalysts (e.g., dibutyltin dilaurate) and polymer stabilizers.<ref name=Ullmann>G. G. Graf "Tin, Tin Alloys, and Tin Compounds" in Ullmann's Encyclopedia of Industrial Chemistry, 2005 Wiley-VCH, Weinheim. {{#invoke:doi|main}}</ref>
Organic synthesisEdit
SnCl4 is used in Friedel–Crafts reactions as a Lewis acid catalyst.<ref name = "Wiberg&Holleman"/> For example, the acetylation of thiophene to give 2-acetylthiophene is promoted by tin(IV) chloride.<ref>Template:Cite journal</ref> Similarly, tin(IV) chloride is useful for nitrations.<ref>Template:Cite journal</ref>
SafetyEdit
Stannic chloride was used as a chemical weapon in World War I, as it formed an irritating (but non-deadly) dense smoke on contact with air. It was supplanted by a mixture of silicon tetrachloride and titanium tetrachloride near the end of the war due to shortages of tin.<ref>Template:Cite book.</ref>