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Piperidine (pip) displaces l,2-bis(diphenylphosphino)ethane (dppe) from mer-(η 2 -C 60 )(η2-dppe)W(CO) 3  to produce mer*-(η 2 -C 60 )(η 1 -ρίρ) 2 \ν(ΟΟ) 3 . The reactions are first order and second order with respect to the molar concentrations of m£r-(r|2-C60)(r|2-dppe)W(CO)3 and pip, respectively. The proposed mechanism, based on the rate law and on the activation parameters, involves an initial pip-assisted ringopening of the dppe ligand to produce the electronically-saturated intermediate fac (η 2 -C 60 )(η'-ρίρ) (n 1 -dppe)W(CO) 3 . This mechanism differs from previously proposed mechanisms for the ligand exchange reactions of closely-related complexes such as/fac-(η 1 -L)(η 2 -dppe)W(CO)3 (L = CO, piperidine, pyridine) and is contrary to the known cis labilizing property of dppe. These results suggest that [60]fullerene has a strong steric influence on the inorganic moiety of the complex and on its chemical behavior.

Site of Bond Breaking in mer-(Dihapto-[60]fullerene) (Dihapto-1,2-Bis-(DiphenyIphosphino)ethane Tricarbonyl Tungsten(0)