A Proton Magnetic Resonance Study of Ligand Exchange on the Hexakis-(N, N-dimethylformamide)magnesium(II) Ion

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Abstract
The rate of ligand exchange on the hexakis(N, N-dimethylformamide) magnesium(II) ion, [Mg(dmf)6]2+, in CD2Cl2 and (CD3)2CO diluents is found to be virtually independent of the concentration of free dmf. This is consistent with a reaction mechanism in which bond rupture is the major factor in the rate-determining step for the exchange process. For a solution in which [Mg(dmf)62+],[dmf] and [CD2Cl,] are 0.0768, 0.397 and 13.9 mol dm-3 respectively, kex(215 K) = 23.5 � 3.2 s-1, ΔH‡ = 77.8 + 3.0 kJ mol-1 and ΔS‡ = l46 � 14 J K-1 mol-1, and similar kinetic parameters characterize other CD2Cl2 solutions. In (CD3)2CO diluent the ligand-exchange process is characterized by smaller ΔH‡ and ΔS‡ values. These data are discussed in conjunction with kinetic data reported for other magnesium(II) systems.

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