An ESR study of the mercuration of the biphenylene radical cation. Evidence for a homolytic mechanism of mercuration
| Autor: | Deborah C. McGuchan, Safieh N. Yazdi, Alwyn G. Davies, John L. Courtneidge |
|---|---|
| Rok vydání: | 1988 |
| Předmět: |
chemistry.chemical_classification
Organic Chemistry Biphenylene Photochemistry Biochemistry Homolysis Inorganic Chemistry chemistry.chemical_compound Deprotonation chemistry Radical ion Electrophile Materials Chemistry Ultraviolet light Trifluoroacetic acid Physical and Theoretical Chemistry Counterion |
| Zdroj: | Journal of Organometallic Chemistry. 341:63-71 |
| ISSN: | 0022-328X |
| Popis: | When a solution of biphenylene in trifluoroacetic acid containing mercury(II) trifluoroacetate is photolysed with ultraviolet light, the ESR spectra show the progressive mercuration of the biphenylene radical cation in the β-position. β-Proton hyperfine coupling [a(Hβ) 3.58 G] is lost, and 199Hg primary, secondary, and tertiary satellites [a(199Hgβ) 76–77 G] appear untl tetra-β-mercuration is complete. It is concluded that, apart from the usual electrophilic mechanism, an alternative mechanism for mercuration exists, and that this probably involves collapse of the aromatic radical cation, ArH+., with its counterion, HgX2-.: ArH + HgX2 → ArH+. + HgX2 → HAr H − X2 → ArHgX + HX |
| Databáze: | OpenAIRE |
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