Abstract

The UV irradiation of (?5-C5Me5)Re(CO)3 in the presence of 1,2,4,5-C6Cl4H2 and 1,3,5-C6Cl3H3 (? = 350 nm, hexane solution) effected intramolecular C-Cl activation, generating the complexes trans-(?5-C5Me5)Re (CO)2(2,4,5-C6Cl5-n Hn)Cl, ((1), n = 2; (2), n = 3), respectively. Complex (1) dissolved in polar organic solvents produces, an equilibrium mixture with its cis isomer. The reaction of (1) with AgBF4, in acetonitrile, led to formation of the cationic complex [cis-(?5-C5Me5)Re (CO)2(2,4,5-C6Cl3H2) (MeCN)]+. The tetramethylfulvene complex (?6-C5Me4CH2)Re (CO)2(2,4,5-C6Cl3H2) (3) was obtained by reacting the cationic complex with the fluorinating agent Et3N · 3HF.