Solvent Bulkiness Effect on N,N-Dimethylformamide Exchange of the o-Phenylenediamine-N,N,N',N'-tetraacetatoferrate(III) Complex as Studied by a High-Pressure NMR Method

Article abstract of DOI:10.1246/bcsj.64.1988

Activation paramaters for solvent exchange of the title complex in N,N-dimethylformamide (DMF) have been determined as follows: k(25 deg C) = (3.4 +/- 0.2) x 10⁷ s^-1, ΔH(excit.) = 18 +/- 3 kJ mol^-1, ΔS(excit.) = -40 +/- 10 J K^-1 mol^-1, and ΔV(excit.) = 10 +/- 2 cm³ mol^-1.The positive value of ΔV(excit.) indicates that the DMF exchange proceeds via a dissociative interchange mechanism.