Abstract
The thermodynamics of ion pair symmetrization in a series of metallocenium species generated from Cp 2 ″ ZrMe 2 ( Cp ″ = 1 , 2 - Me 2 C 5 H 3 ) were studied using a variety of solution dynamic techniques including line broadening, 2D-EXSY, and 1D-DPFGSE-NOE. Ion pairs were generated by methide abstraction using the corresponding trityl salts [ 1-A] to yield [ Cp 2 ″ ZrMe ] + [ A ] - (A = {C 6F 4-1,2-[B(C 6F 5) 2] 2(μ-O(C 6F 5))} −, 2-O(C 6 F 5 ); {C 6F 4-1,2-[B(C 6F 5) 2] 2(μ-OPh)} −, 2-OPh; {C 6F 4-1,2-[B(C 6F 5) 2] 2(μ-OMe)} −, 2-OMe; and [B(C 6F 5) 4] −, 2-B(C 6 F 5 ) 4 ). The observed activation parameters were interpreted on the basis of a solvent-assisted mechanism of ion pair symmetrization.
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