The arene ligand in the complex TpRe(CO)(Melm)(eta(2)-benzene) (Tp = hydridotris(pyrazolyl)borate; Melm = N-methylimidazole) undergoes tandem electrophile/nucleophile 1,4-addition reactions. Subsequent oxidative demetalation affords cis-3,6-disubstituted 1,4-cyclohexadienes (46-84%). Common organic electrophiles such as acetals and Michael acceptors were successfully added to the bound benzene to generate eta(3)-benzenium complexes, which then were treated with a silyl ketene acetal, silyl vinyl ether, phenyllithium, or malonate ester to afford 1,4-dialkylated dihydrobenzene complexes. The d(6) transition metal analogues TpW(NO)(PMe3)(eta(2)-benzene) and [Os(NH3)(5)(eta(2)-benzene)](2+) also undergo 1,4-dialkylation reactions, and the relative ability of all three metals to activate arenes is compared.