Syntheses and reactions of the complexes (eta(5)-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-C 6Cl4H2 and 1,3,5-C6Cl3H3 (lambda = 350 nm, hexane solution) effected intram olecular 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 wi th 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-C6Cl3 H2)(MeCN)](+). The tetramethylfulvene complex (eta (6)-C5Me4CH2)Re(CO)(2)(2 ,4,5-C6Cl3H2) (3) was obtained by reacting the cationic complex with the fl uorinating agent Et3N . 3HF.