The fluoro analogue of Wilkinson's catalyst and unexpected Ph-Cl activation.
The fluoro analogue of Wilkinson's catalyst, [(Ph3P)3RhF] (1), was synthesized and fully characterized. Both solution behavior and solid-state geometry parameters of 1 were found to be surprisingly similar to those of Wilkinson's catalyst. Unlike Wilkinson's catalyst however, 1 exhibited most unusual reactivity toward the notoriously inert C-Cl bond of nonactivated chloroarenes. The novel Ph-Cl activation with 1 includes fluorine transfer from the metal to a phosphine ligand and evidently phenyl transfer from the phosphine to Rh to produce an electron-rich sigma-phenylrhodium intermediate.
Grushin
Vladimir V
VV
Central Research & Development, E. I. DuPont de Nemours and Co., Inc., Experimental Station, Wilmington, Delaware 19880-0328, USA. vlad.grushin-1@usa.dupont.com
Marshall
William J
WJ