Facile carbon-fluorine bond activation and subsequent functionalisation of 1,1-difluoroethylene and tetrafluoroethylene promoted by adjacent metal centres
| Autor: | Michael E. Slaney, Dusan Ristic-Petrovic, D. Jason Anderson, Robert McDonald, Martin R. Cowie |
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| Rok vydání: | 2011 |
| Předmět: |
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Molecular Magnetic Resonance Spectroscopy Vinyl Compounds chemistry.chemical_element Alkenes Crystallography X-Ray Iridium Ligands Medicinal chemistry Catalysis Metal chemistry.chemical_compound Organometallic Compounds Organic chemistry Olefin fiber Fluorocarbons Molecular Structure Chemistry Ligand Organic Chemistry General Chemistry Fluorine 1 1-Difluoroethylene Carbon Metals visual_art visual_art.visual_art_medium Tetrafluoroethylene Fluoride Carbon monoxide |
| Zdroj: | Chemistry (Weinheim an der Bergstrasse, Germany). 18(15) |
| ISSN: | 1521-3765 |
| Popis: | The bridging fluoroolefin ligands in the complexes [Ir(2)(CH(3))(CO)(2)(μ-olefin)(dppm)(2)][OTf] (olefin = tetrafluoroethylene, 1,1-difluoroethylene; dppm = μ-Ph(2)PCH(2)PPh(2); OTf(-) = CF(3)SO(3)(-)) are susceptible to facile fluoride ion abstraction. Both fluoroolefin complexes react with trimethylsilyltriflate (Me(3)SiOTf) to give the corresponding fluorovinyl products by abstraction of a single fluoride ion. Although the trifluorovinyl ligand is bound to one metal, the monofluorovinyl group is bridging, bound to one metal through carbon and to the other metal through a dative bond from fluorine. Addition of two equivalents of Me(3)SiOTf to the tetrafluoroethylene-bridged species gives the difluorovinylidene-bridged product [Ir(2)(CH(3))(OTf)(CO)(2)(μ-OTf)(μ-C=CF(2))(dppm)(2)][OTf]. The 1,1-difluoroethylene species is exceedingly reactive, reacting with water to give 2-fluoropropene and [Ir(2)(CO)(2)(μ-OH)(dppm)(2)][OTf] and with carbon monoxide to give [Ir(2)(CO)(3)(μ-κ(1):η(2)-C≡CCH(3))(dppm)(2)][OTf] together with two equivalents of HF. The trifluorovinyl product [Ir(2)(κ(1)-C(2)F(3))(OTf)(CO)(2)(μ-H)(μ-CH(2))(dppm)(2)][OTf], obtained through single C-F bond activation of the tetrafluoroethylene-bridged complex, reacts with H(2) to form trifluoroethylene, allowing the facile replacement of one fluorine in C(2)F(4) with hydrogen. |
| Databáze: | OpenAIRE |
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