Abstract
The authors have previously studied acetic acid exchange on perchlorates of manganese(II), iron(II), cobalt(II), nickel(II), and copper(II) ions in acetic acid (HOAc). These metal(II) perchlorates in acetic acid exist as hexasolventometal ions that form ion pairs with perchlorate anion. On the other hand, acetate ion (OAc/sup -/) in transition-metal(II) acetates is bound to the central metal ions in acetic acid. Thus, they expect that coordinated acetate ion exerts some effect on the solvent-exchange rate, i.e., bound-ligand effect. In this work rates of acetic acid exchange on Mn(OAc)/sub 2/, Co(OAc)/sub 2/, and Cu/sub 2/(OAc)/sub 4/ (tetrakis(..mu..-acetato)dicopper(II)) in acetic acid and mixtures with dichloromethane-d/sub 2/ as an inert cosolvent were measured by means of the oxygen-17 NMR line-broadening method. The activation parameters obtained are compared with those for the corresponding perchlorates.
Published Version
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