Perfluoroalkyl phosphinic acids

M. B. Herath, S. E. Creager, A. Kitaygorodskiy, D. D. DesMarteau, ChemPhysChem 2010, 11, 2871-2878. Perfluoroalkyl phosphonic and phosphinic acids as proton conductors for anhydrous proton-exchange membranes. 

Codeposition of silver vapor with perfluoroalkyl iodides at -196 °C provides an alternative route to nonsolvated primary perfluoroalkylsilvers [272] Phosphine complexes of trifluaromethylsilver are formed from the reaction of trimethyl-phosphme, silver acetate, and bis(trifluoromethyl)cadmium glyme [755] The per-fluoroalkylsilver compounds react with halogens [270], carbon dioxide [274], allyl halides [270, 274], mineral acids and water [275], and nitrosyl chloride [276] to give the expected products Oxidation with dioxygen gives ketones [270] or acyl halides [270] Sulfur reacts via insertion of sulfur into the carbon-silver bond [270] (equation 188)... 

In addition to the perfluoroalkylation of arenes Pd(dba)2 competently facilities the ortho-C-H amination of A-aryl benzamides with electrophilic 0-benzoyl hydroxylamines. Pd(dba)2 showed equal reactivity to other precatalysts, such as Pd(OAc)2. Although mechanistically unclear, the addition of AgOAc signiflcantly improved conversion, while the addition of external phosphine ligands was detrimental. Finally, the 4-CF3(C6p4) directing group was optimal because acidic N-H bonds are essential for this transformation (eq 36). ... 

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