Pentaphenylbismuth
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Pentaphenyl-λ5-bismuthane | |
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| Properties | |
| Bi(C6H5)5 | |
| Molar mass | 594.510 g·mol−1 |
| Appearance | Violet crystals |
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Except where otherwise noted, data are given for materials in their standard state (at 25 °C [77 °F], 100 kPa).
Infobox references
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Pentaphenylbismuth is an organobismuth compound with formula Bi(C6H5)5, often abbreviated as BiPh5, where Ph stands for phenyl. It is a violet crystalline solid. A molecule of pentaphenylbismuth consists of five phenyl groups attached to one bismuth atom. In this compound, bismuth is hypervalent.
History
Pentaphenylbismuth was prepared by Georg Wittig et al. and his coworker K. Clauss in 1952.[1]
Synthesis
Pentaphenylbismuth can be synthesized by reaction of triphenylbismuth dichloride with phenyllithium.[2]
- Ph3BiCl2 + 2 PhLi → BiPh5 + 2 LiCl
Triphenylbismuth dichloride itself can be synthesized by oxidation of triphenylbismuth by sulfuryl chloride.[3]
- BiPh3 + SO2Cl2 → Ph3BiCl2 + SO2
Structure
A strong violet color and strong dichroism of pentaphenylbismuth are very unusual for a compound of a main-group element. Bismith's lighter congeners, like antimony, never displays such behavior, nor when the bismuth's symmetry is D3h. The X-ray structure analysis done at −96 °C (−141 °F) shows that Bi(C6H5)5 has a square pyramidal molecular geometry and is thus very similar to the colorless Sb(C6H5)5, which also has the same molecular geometry.[4][1]
Uses
Pentaphenylbismuth is a useful reagent for the ortho-phenylation of phenols under mild conditions.[5]
Reactions
Pentaphenylbismuth reacts with sulfur dioxide to give diphenylsulfone under mild conditions in high yield.[6]
Pentaphenylbismuth easily forms a bismuthonium cation, for example by reaction with p-toluenesulfonic acid:[7]
- BiPh5 + ArSO2OH → [BiPh4]+[ArSO3]−
Pentaphenylbismuth forms an ate complex upon reaction with phenyl lithium:[8]
- BiPh5 + PhLi → Li+[BiPh6]−
References
- ^ a b El-Issa, B. D.; Pyykko, P.; Zanati, H. M. (1991). "MS X.alpha. Studies on the colors of pentaphenylbismuth, hexachloroplumbate(2-) and tetrathiotungstate(2-): Are relativistic effects on the LUMO important?". Inorganic Chemistry. 30 (13): 2781–2787. doi:10.1021/ic00013a015.
- ^ R., King (2005). Encyclopedia of Inorganic Chemistry. Vol. I: A-C (2nd ed.). Wiley. pp. 345–369. ISBN 9780470860786.
- ^ Organobismuth Chemistry. Elsevier Science. 1 January 2001. pp. 247–327. Retrieved 4 March 2026 – via www.sciencedirect.com.
- ^ Schmuck, Arno; Buschmann, Jürgen; Fuchs, Joachim; Seppelt, Konrad (4 November 1987). "Structure and Color of Pentaphenylbismuth". Angewandte Chemie International Edition in English. 26 (11): 1180–1182. doi:10.1002/anie.198711801. Retrieved 4 March 2026 – via CrossRef.
- ^ Barton, Derek H. R.; Blazejewski, Jean-Claude; Charpiot, Brigitte; Lester, David J.; Motherwell, William B.; Papoula, M. Teresa Barros (1980). "Comparative arylation reactions with pentaphenylbismuth and with triphenylbismuth carbonate". Journal of the Chemical Society, Chemical Communications (17): 827. doi:10.1039/C39800000827.
- ^ Sharutin, V. V.; Ermoshkin, A. E. (1 November 1987). "Phenylation of sulfur dioxide by pentaphenylbismuth". Bulletin of the Academy of Sciences of the USSR, Division of Chemical Science. 36 (11): 2414. doi:10.1007/BF00957333. Retrieved 4 March 2026 – via Springer Link.
- ^ Barton, Derek H. R.; Charpiot, Brigitte; Dau, Elise Tran Huu; Motherwell, William B.; Pascard, Claudine; Pichon, Clotilde (14 March 1984). "Structural Studies of Crystalline Pentacalent Organobismuth Compounds". Helvetica Chimica Acta. 67 (2): 586–599. doi:10.1002/hlca.19840670227.
- ^ Wallenhauer, Stephan; Leopold, Dieter; Seppelt, Konrad (September 1993). "Hexacoordinate organobismuth compounds". Inorganic Chemistry. 32 (18): 3948–3951. doi:10.1021/ic00070a029.