Organoantimony chemistry is the chemistry of compounds containing a carbon to antimony (Sb) chemical bond. Relevant oxidation states are SbV and SbIII. The toxicity of antimony limits practical application in organic chemistry.

Syntheses

Stibines

An organoantimony synthesis typically begins with tricoordinate antimony compounds, called stibines. Antimony trichloride reacts with organolithium or Grignard reagents to give compounds of the form R3Sb: Stibines are weak Lewis acids and do not form ate complexes. As soft Lewis donors, they see wide use in coordination chemistry and typically react through oxidative addition: This property also sensitizes them to air. If reduced instead, stibanes typically release substituents (ligands): The cyclic compound stibole, a structural analog of pyrrole, has not been isolated, but substituted derivatives have. Antimony metallocenes are known as well: The Cp*-Sb-Cp* angle is 154°.

Stiboranes

Pentacoordinate antimony compounds are called stiboranes, and can be synthesised from stibines and halogens: Like their heavier congeners, the organobismuth compounds, stiboranes form onium compounds and ate complexes. Asymmetric compounds can also be obtained through the stibonium ion: Stibonium halides (R4SbX) tend to dimerize. Trigonal-bipyramidal molecule pentaphenylantimony decomposes at 200 °C to triphenylstibine and biphenyl. In the related Me5Sb, proton NMR at -100 °C cannot resolve different methyl protons.

Distibines and antimony(I) compounds

Distibines are formally SbII compounds, but feature tricoordinate Sb atoms with a single Sb-Sb bond. They may have interest as thermochromes. For example, tetramethyldistibine is colorless when gas, yellow when liquid, red when solid just below the melting point of 18.5 °C, shiny-blue when cooler, and again yellow at cryogenic temperatures. A typical synthesis first displaces an SbIII halide with an alkali metal and then reduces the resulting anion with ethylene dichloride. Like its lighter congener, arsenic, organoantimony compounds can be reduced to cyclic oligomers that are formally antimony(I) compounds.

With other substituents

SbV-N bonds are unstable, except where the N is also bonded to other electron-withdrawing substituents.

Reactions

Stibine oxides undergo a sort of polarized-olefin metathesis. For example, they mediate a carbonyl-imine exchange (Ar is any activated arene): "Ph3Sb=NSO2Ar + PhC=O → Ph3Sb=O + PhC=NSO2Ar"The effect may extend vinylically: In contrast, unstabilized ylides (R3Sb=CR'2; R' not electron-withdrawing) form only with difficulty (e.g. diazo reagents). Like other metals, stibanes vicinal to a leaving group can eliminate before a proton. For example, diphenyl(β-hydroxyphenethyl)stibine decomposes in heat or acid to styrene: As tertiary stibines also insert into haloalkyl bonds, tertiary stibines are powerful dehalogenating agents. However, stibanes poorly imitate active metal organometallics: only with difficulty do their ligands add to carbonyls or they power noble-metal cross couplings. Stiboranes are gentle oxidants, converting acyloins to diketones and thiols to disulfides. In air, tris(thiophenyl)stibine catalyzes a Hunsdiecker-like decarboxylative oxidation of anhydrides to alcohols. In ultraviolet light, distibines radicalize; the resulting radicals can displace iodide.