Fluoroalkenyl, fluoroalkynyl and fluoroalkyl phosphines

Expanding the carbo‐Benzene Chemical Space for Electron‐Accepting Ability: Trifluorotolyl/Tertiobutyl Substitution Balance

“…6 Further computational and experimental investigations along these lines are under current progress. 5 This is appraised, for example, by the relative Tolman electronic parameter of the P(CF 3 ) 3 , P(C 6 F 5 ) 3 , and PF 3 ligands in Ni(CO) 4 complexes: ν CO [P(C 6 F 5 ) 3 ] = 2091 cm À 1 vs. ν CO [P(CF 3 ) 3 ] = 2107 cm À 1 vs. ν CO [PF 3 ] = 2111 cm À 1 , over a 2056-2111 cm À 1 value range: see [32] and references therein. 6 See the Supporting Information of reference [12].…”

Synthesis and Properties of Perfluoroalkyl Phosphine Ligands: Photoinduced Reaction of Diphosphines with Perfluoroalkyl Iodides

“…The absorption maxima (l max ) of the perfluoroalkyl iodides and tetraphenyldiphosphine are 270 nm [6] and 260 nm, [11] respectively, and the absorption reaches the near-UV region. [13] The 31 P-77 Se coupling constant ( 1 J P-Se ) is known to be correlated with the electronic properties of the phosphine, that is, a large 1 J P-Se value reflects the poor electron-donating ability of the phosphine. The perfluoroalkyl radical generated by the cleavage of perfluoroalkyl iodide reacts with the diphosphine to form the perfluoroalkyl phosphine 2 and a phosphine radical.…”

“…The perfluoroalkyl group in 2 is directly substituted at the phosphorus atom and hence may have a marked electronic effect. [13] The 31 P-77 Se coupling constant ( 1 J P-Se ) is known to be correlated with the electronic properties of the phosphine, that is, a large 1 J P-Se value reflects the poor electron-donating ability of the phosphine. [14] Hence, we measured 1 J P-Se for several phosphines (see Table S1 in the Supporting Information).…”

Synthesis and Properties of Perfluoroalkyl Phosphine Ligands: Photoinduced Reaction of Diphosphines with Perfluoroalkyl Iodides

“…Next, we investigated the electronic properties of 2 because they actually estimate the efficiency of the transition‐metal catalyst. The perfluoroalkyl group in 2 is directly substituted at the phosphorus atom and hence may have a marked electronic effect 13. The 31 P‐ 77 Se coupling constant ( 1 J P‐Se ) is known to be correlated with the electronic properties of the phosphine, that is, a large 1 J P‐Se value reflects the poor electron‐donating ability of the phosphine 14.…”