Proton Relaxation in Dilute Solutions of Cobalt(II) and Nickel(II) Ions in Methanol and the Rate of Methanol Exchange of the Solvation Sphere

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Abstract
The nuclear relaxation of the hydroxyl and methyl protons in methanol containing low concentrations of Co++ and Ni++ ions has been investigated between —80°C and +80°C. This work complements previous studies of the NMR spectra of the solvation complexes in similar solutions. Over the temperature range studied, the relaxation due to the dissolved paramagnetic ions changes over two or three orders of magnitude. This dependence, as well as a corresponding temperature dependence of the chemical shift of the methanol peaks, can be quantitatively interpreted in terms of chemical exchange of methanol molecules between the coordination sphere of the paramagnetic ions and the bulk methanol. It is found that the dominant exchange process involves whole methanol molecules, i.e., proton transfer is relatively unimportant. The exchange rate is characterized by ΔH‡=13.8 kcal mole—1 and ΔS‡=+7.2 eu for Co++ ions; and ΔH‡=15.8 kcal per mole and ΔS‡=+8.0 eu for Ni++ ions. The hyperfine interaction between the paramagnetic ion and a methanol molecule in the coordination sphere is for Co++:+4.1×105 cps for the CH3 protons, and +80×105 cps for the OH proton; the corresponding numbers for Ni++ are: +5.7×105 cps and +6.8×105 cps. Proton relaxation times of the methanol in the coordination sphere are also obtained.