Electron transfer reactions involving trans-[PtH2(PCy3)2] and fluorinated benzonitriles
| Autor: | Paul S. Pregosin, Samuel Hintermann, Howard C. Clark, Heinz Rüegger |
|---|---|
| Rok vydání: | 1992 |
| Předmět: |
Reaction mechanism
Nitrile Chemistry Stereochemistry Aryl Organic Chemistry chemistry.chemical_element Tricyclohexylphosphine Nuclear magnetic resonance spectroscopy Biochemistry Medicinal chemistry Inorganic Chemistry Reaction rate Electron transfer chemistry.chemical_compound Materials Chemistry Physical and Theoretical Chemistry Platinum |
| Zdroj: | Journal of Organometallic Chemistry. 435:225-234 |
| ISSN: | 0022-328X |
| Popis: | The complex trans-[PtH2(PCy3)2] reacts with activated benzonitriles such as 4-R-C6F4CN (R = F, H, CN, OCH3) bearing electron-withdrawing substituents to give the new platinum(II) aryl complexes trans-[PtHRC6F3CN(PCy3)2], which have been isolated and fully characterized, and a hydridofluoride trans-[PtH(“F”)(PCy3)2], where “F” is either F or HF2, which has been detected in solution. These complexes and related by-products from the reaction have been characterized by one- and two-dimensional multinuclear NMR spectroscopy. A reaction mechanism involving rate-determining electron transfer from the dihydride complex to the organic substrate is postulated on the basis of (i) the relative reaction rates for the nitriles (p-C6F4(CN)2 > C6F5CN > p-C6HF4CN > p-C6F4(OCH3)CN > o,o-C6H3F2CN), which parallel their electron affinities, and (ii) the observation of a radical by ESR spectroscopy after “spin-trapping” with PBN. |
| Databáze: | OpenAIRE |
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