Facile Ar-CF3 bond formation at Pd. Strikingly different outcomes of reductive elimination from [(Ph3P)2Pd(CF3)Ph] and [(Xantphos)Pd(CF3)Ph].
Facile and highly selective perfluoroalkyl-aryl reductive elimination from a metal center (Pd) has been demonstrated for the first time. At temperatures as low as 50-80 degrees C, [(Xantphos)Pd(Ph)CF3] undergoes remarkably clean decomposition to produce CF3Ph in high yield and selectivity. In contrast, analogous trifluoromethylpalladium aryls stabilized by rigid cis-chelating ligands such as dppe are completely unreactive at temperatures up to 130-140 degrees C. Decomposition of [(Ph3P)2Pd(Ph)CF3] in the presence of PhI in benzene at 60 degrees C does not produce PhCF3 but rather leads to [(Ph3P)2Pd(Ph)I] and [Ph4P]+[(Ph3P)Pd(CF3)3]- in a 2:1 ratio with high selectivity.
Grushin
Vladimir V
VV
Central Research & Development, E. I. DuPont de Nemours and Co., Inc., Experimental Station, Wilmington, DE 19880-0328, USA. vlad.grushin-1@usa.dupont.com
Marshall
William J
WJ
D018360:Crystallography, X-Ray; D006845:Hydrocarbons, Fluorinated / Q000138:chemical synthesis / Q000737:chemistry*; D009942:Organometallic Compounds / Q000138:chemical synthesis / Q000737:chemistry*; D010165:Palladium / Q000737:chemistry*; D010720:Phosphines / Q000138:chemical synthesis / Q000737:chemistry*; D014966:Xanthenes / Q000737:chemistry*
D006845:Hydrocarbons, Fluorinated; D009942:Organometallic Compounds; D010720:Phosphines; D014966:Xanthenes; D010165:Palladium; C519861:xantphos