RESUMO
Perfluoroalkyl Grignard reagents react with phosphoryl halides at -78 °C to room temperature to selectively produce bis(perfluoroalkyl)phosphonyl halides, which after aqueous work up, give bis(perfluoroalkyl)phosphinic acids in high overall yields. Reaction of perfluoroalkyl Grignards with phenylphosphonic dichloride gives high yields of bis(perfluoroalkyl)phenyl phosphine oxides which are readily hydrolysed to perfluoroalkyl(phenyl)phosphinic acids.
RESUMO
The reaction of perfluoroalkyl Grignard reagents with phosphorus(III) halides was explored. In the process a new convenient, one-pot, high yield method for the synthesis of (perfluoroalkyl)phosphonic acids has been developed. Perfluoroalkyl Grignard reagents react with phosphorus trichloride or phosphorus tribromide to form (perfluoroalkyl)phosphonous dihalides. Hydrolysis gives the corresponding (perfluoroalkyl)phosphonous acids. Oxidation of the phosphonous acids with H(2)O(2) produces (perfluoroalkyl)phosphonic acids in 60-78% overall yields, based on the corresponding perfluoroalkyl iodide. The X-ray crystal structures of the toluidinium salts, [MeC(6)H(4)NH(3)](2)[C(2)F(5)PO(3)] and [MeC(6)H(4)NH(3)][C(8)F(17)P(O)(2)OH], are reported.
RESUMO
We report a one-step synthesis of the phosphine, PPh(2)(i)C(3)F(7) from commercially available precursors. The stereoelectronic properties of the phosphine were probed by coordination to transition metals. Mo(CO)(5)PPh(2)(i)C(3)F(7) was synthesised and the synthesis and structure of trans-PtCl(2)(PPh(2)(i)C(3)F(7))(2) are described. PPh(2)(i)C(3)F(7) was found to be a bulky electron-withdrawing ligand.
Assuntos
Complexos de Coordenação/síntese química , Fosfinas/química , Fosfinas/síntese química , Complexos de Coordenação/química , Cristalografia por Raios X , Conformação Molecular , Estereoisomerismo , Elementos de TransiçãoRESUMO
Simple chlorodiisopropylphosphine adducts of rhodium, either pre-formed or formed in situ, prove to be highly effective catalysts for the ortho-arylation of phenols.
Assuntos
Compostos Organometálicos/química , Fenóis/síntese química , Fosfinas/química , Propano/análogos & derivados , Ródio/química , Catálise , Cristalografia por Raios X , Ligantes , Modelos Moleculares , Estrutura Molecular , Compostos Organometálicos/síntese química , Fenóis/química , Propano/químicaRESUMO
Tris(perfluoroalkyl)phosphines, of interest as tunable alternatives to the carbon monoxide ligand, can be synthesised by the nucleophile mediated reaction of perfluoroalkyltrimethylsilanes with triphenylphosphite; the method can be extended to diphosphines.
