Generation of the dichloromethane complex [(η 5-C 5Me 5)Re(NO)(PPh 3)(ClCH 2Cl] + BF 4−, and its conversion to the oxidative addition product [(η 5-C 5Me 5)Re(NO)(PPh 3)(Cl)(CH 2Cl)] + BF 4−

Abstract

Reaction of (η 5-C 5Me 5)Re(NO)(PPh 3)(CH 3) and HBF 4 · OEt 2 in CH 2Cl 2 at −78°C gives the dichloromethane complex [η 5-C 5Me 5Re(NO)(PPh 3)(ClCH 2Cl)] + BF 4 −, which undergoes the title transformation at −35°C. The ReClCH 2Cl carbon is attacked by halide nucleophiles (X −) to give XCH 2Cl and the chloride complex (η 5-C 5Me 5)Re(NO)(PPh 3)(Cl), and exhibits a 13C NMR resonance that is coupled to phosphorus (d, 3 J(CP) 5.0 Hz) and geminal hydrogens (t, 1 J(CH) 186 Hz).