triphenylphosphine in tetrahydrofuran Kinetics; byproducts: THF; 15-40°C; phosphine concn. 1.2E-2 to 16.4E-2 M; pressure 1-100 MPa;

n-BuLi in dichloromethane under N2 or Ar; n-BuLi in hexane added (-80°C) to alkyne in THF; stirred (-80°C, 20 min); Cr complex in THF added; stirred (ambient temp., 30 min); solvent removed; dissolved in CH2Cl2; treated with Et3OBF4 (0°C); stirred (60 min); filtered at -20°C through silica layer using CH2Cl2 as eluent; solvent evapd.; sepd. by chromy. (silica, -20°C, pentane-CH2Cl2 2:1, 1:1 to 1:3); elem. anal.;

n-BuLi in dichloromethane under N2 or Ar; n-BuLi in hexane added (-80°C) to alkyne in THF; stirred (-80°C, 20 min); Cr complex in THF added; stirred (ambient temp., 30 min); solvent removed; dissolved in CH2Cl2; treated with Me3OBF4 (0°C); stirred (60 min); filtered at -20°C through silica layer using CH2Cl2 as eluent; solvent evapd.; sepd. by chromy. (silica, -20°C, pentane-CH2Cl2 2:1, 1:1 to 1:3); elem. anal.;

in tetrahydrofuran inert atmosphere; stirring for 12 h at 25°C; evapn., removal of Cr(CO)6 (1E-2 Torr, 40°C); NMR spectroscopy;

n-BuLi in dichloromethane under N2 or Ar; n-BuLi in hexane added (-80°C) to alkyne in THF; stirred (-100°C, 20 min); Cr complex in THF added; stirred (ambient temp., 30 min); solvent removed; dissolved in CH2Cl2; treated with Et3OBF4 (0°C); stirred (60 min); filtered at -20°C through silica layer using CH2Cl2 as eluent; solvent evapd.; sepd. by chromy. (silica, -20°C, pentane-CH2Cl2 2:1, 1:1 to 1:3, 1:4); elem. anal.;

n-BuLi in dichloromethane under N2 or Ar; n-BuLi in hexane added (-80°C) to alkyne in THF; stirred (-100°C, 20 min); Cr complex in THF added; stirred (ambient temp., 30 min); solvent removed; dissolved in CH2Cl2; treated with Et3OBF4 (0°C); stirred (60 min); filtered at -20°C through silica layer using CH2Cl2 as eluent; solvent evapd.; sepd. by chromy. (silica, -20°C, pentane-CH2Cl2 2:1, 1:1 to 1:3, 1:4); elem. anal.;

1: n-C4H9Li / tetrahydrofuran; hexane 2: tetrahydrofuran 3: air / dichloromethane View Scheme

in tetrahydrofuran equimolar organic ligand added to THF soln. of Cr-complex; react. mixt. stirred at ambient temp.; solvent removed in vacuo; residue chromatographed on silica gel at -20°C using pentane/CH2Cl2 as eluent; elem. anal.;

in tetrahydrofuran equimolar organic ligand added to THF soln. of Cr-complex; react. mixt. stirred at ambient temp.; solvent removed in vacuo; residue chromatographed on silica gel at -20°C using pentane/CH2Cl2 as eluent; elem. anal.;

in tetrahydrofuran Ar atmosphere, addn. of Rh complex to soln. of Cr complex and P4, stirring (room temp., 10 min), concn. to dryness (70°C, vacuum); sublimation (50°C, vacuum), suspn. (n-pentane), filtration, extn.with hot filtrate, concn. (vacuum), crystn. (5°C), sublimation ( 60°C, vacuum), crystn. (CH2Cl2, 0°C), dissolution of extd.solid (CH2Cl2), crystn. (0°C);