Abstract
Tri-n-butylphosphine, tri-n-butylphosphite, and imidazole add to the cycloheptatriene ring in (C 7H 8)FeCp) + (I) to give cycloheptadienyl adducts (II). The second order rate constants ( M −1 s −1) in acetone at 25°C are: P(OBu) 3, 0.50; PBu 3, 2250; HIm, 67. The relative nucleophilic reactivities are the same as that found with other coordinated cyclic π-hydrocarbons and with free carbocations. This further supports the recent suggestion [1] that a Ritchie type correlation holds for attack on all complexes of the form (ring)ML n. The Fe(Cp) + moiety is 11,000 times weaker than Mn(CO) 3 + in activating coordinated cycloheptatriene. NaBH 4, MeLi, and NaCH(CO 2Et) 2 also add to the ring in I, indicating that I may have synthetic utility.
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