We present a mechanistic study demonstrating selective Arf-Cl bond activation preceded by η2 coordination of Pd(PEt 3)2 to a C=C moiety of a partially fluorinated substrate. An intramolecular ring-walking process to activate the Arf-Cl bond is plausible, but an intermolecular reaction becomes dominant in the presence of PEt3. The latter pathway is significantly enhanced, since PEt 3 promotes dissociation of Pd(PEt3)3 from the C=C moiety followed by activation of the Arf-Cl bond. Our observations also show that PEt3 can be used to control reaction selectivity. The experimental observations are supported by density functional theory (DFT) calculations (at the SMD(toluene)-DSD-PBEP86/cc-pV(D+d)Z-PP//DF- PBE+dv2/SDD(d) level of theory).
ASJC Scopus subject areas
- Physical and Theoretical Chemistry
- Organic Chemistry
- Inorganic Chemistry