Syntheses and reactions of the complexes (η5-C5Me5)Re(CO)2(C6Cl5-nHn)Cl (n=2,3):: Compounds derived from initial C-Cl activation

The UV irradiation of (eta (5)-C5Me5)Re(CO)(3) in the presence of 1,2,4,5-C6Cl4H2 and 1,3,5-C6Cl3H3 (lambda = 350 nm, hexane solution) effected intramolecular C-Cl activation, generating the complexes trans-(eta (5)-C5Me5)Re(CO)(2)(2,4,5-C6Cl5-nHn)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-(eta (5)-C5Me5)Re(CO)(2)(2,4,5-C6Cl3H2)(MeCN)](+). The tetramethylfulvene complex (eta (6)-C5Me4CH2)Re(CO)(2)(2,4,5-C6Cl3H2) (3) was obtained by reacting the cationic complex with the fluorinating agent Et3N . 3HF.