Organoantimony chemistry is the chemistry of compounds containing a carbon to antimony (Sb) chemical bond. Relevant oxidation states are Sb(V) and Sb(III). The toxicity of antimony1 limits practical application in organic chemistry.2
Antimony compounds of the type R5Sb (stiboranes) can be synthesised from trivalent Sb precursors:
- Ph3Sb + Cl2 → Ph3SbCl2
- Ph3SbCl2 + 2 PhLi → Ph5Sb
Asymmetric compounds can also be obtained through the stibonium ion:
- R5Sb + X2 → [R4Sb]+[X]
- [R4Sb]+[X] + R'MgX → R4R'Sb
Pentaphenylantimony decomposes at 200 °C to triphenylstibine and biphenyl. It forms a trigonal bipyramidal molecular geometry. In the related Me5Sb all methyl protons are equivalent at -100 °C in proton NMR. Compounds of the type R4SbX tend to form dimers.
- SbCl3 + 3 RLi (or RMgCl) → R3Sb
Typical reactions are:
- R3Sb + Br2 → R3SbBr2
- R3Sb + O2 → R3SbO
- R3Sb + Na + NH3 → R2SbNa
- R3Sb + B2H6 → R3Sb·BH3
Stibanes are weak Lewis acids and therefore ate complexes are not encountered. On the other hand, they have good donor properties and are therefore widely used in coordination chemistry. R3Sb compounds are more air-sensitive than the R5Sb counterparts.
Antimony Metallocenes are known as well:
- 14SbI3 + 3 (Cp*Al)4 → [2Cp*Sb]+[AlI4− + 8Sb + 6 AlI3
The Cp*-Sb-Cp* angle is 154°.
Distibines have a Sb-Sb single bond and are of some interest as thermochromic materials. For example, tetramethyldistibine is a colorless as a gas, yellow as a liquid, red as solid just below the melting point of 18.5 °C and again yellow well below the melting point.3
- Chemical bonds of carbon with other elements in the periodic table:
- Filella, M. "Alkyl derivatives of antimony in the environment". Metal ions in life sciences (Cambridge: RSC publishing) 7: 267–301. doi:10.1039/9781849730822-00267. ISBN 978-1-84755-177-1.
- C. Elschenbroich, A. Salzer Organometallics : A Concise Introduction (2nd Ed) (1992) from Wiley-VCH: Weinheim. ISBN 3-527-28165-7
- Organoantimony compounds with element-element bonds H.J. Breunig, R. Rosler Coordination Chemistry Reviews 163 (1997) 33-53