Syntheses and Characterization of the First Cycloheptatrienyl Transition-Metal Complexes with a M-CF(3) Bond

The organometallic chemistry of metal complexes with organocyclic ligands of higher than five hapticity is much more lacking than the chemistry of metal complexes with η(5)-cyclopentadienyl ligands, which has been explored in considerable depth, resulting in novel advances. The main reason for this is stability. In particular, reports indicate that (η(7)-C(7)H(7))ML(n) complexes are considerably less stable than analogous (η(5)-C(5)H(5))ML(n). In perfluoroalkyl metal chemistry, there is currently no reported (η(7)-C(7)H(7))ML(n) derivative, whereas a number of alkylated ones are known and important conclusions have been drawn about their stability. Responding to this void, and using Morrison’s trifluoromethylating reagent, the present study reports the synthesis and characterization of the first cycloheptatrienyl molybdenum complexes bearing the trifluoromethyl moiety; (η(7)-C(7)H(7))Mo(CO)(2)CF(3) (I), and (η(7)-C(7)H(7))Mo(CO)(PMe(3))CF(3) (II) and discusses their low thermal instability.