Evidence for ionic samarium(II) species in THF/HMPA solution and investigation of their electron-donating properties

The fundamental nature of samarium(II) complexes in THF/HMPA (HMPA = hexamethylphosphoramide) solutions containing SmI2 has been clarified by means of cyclic voltammetry, conductivity measurements, UV spectroscopy, and kinetic measurements. The principal species is not [SmI2(hmpa)4] as previously suggested, but either the ionic cluster [Sm(hmpa)4(thf)2+2I- if four equivalents of HMPA is present in the THF solution or [Sm(hmpa)6]2+ 2I- in the presence of at least 10 equivalents of HMPA. The formal potential of the [Sm(hmpa)4(thf)2]3+ 2I-/[Sm(hmpa)4(thf)2]2- 2I- redox couple determined by cyclic voltammetry was -1.79 +/- 0.08 V versus SCE. The order of reactivity of the samarium(II) complexes was found to be [Sm(hmpa)6]2+2I- > [Sm(hmpa)4(thf)2]2+2I- > SmI2 in their respective reactions with 1-iodobutane and with benzyl chloride. Very high rate enhancements, of the order of 1,000-15,000-fold, were observed upon addition of HMPA to the THF solution containing SmI2, Comparison of these rate constants with the corresponding rate constants for electron transfer (ET) reactions involving aromatic radical anions revealed that none of the reactions studied can be classified as outer-sphere ET processes and that the inner-sphere electron-donating abilities of the [Sm(hmpa)4(thf)2]2+ 2I- and SmI2 complexes are comparable. The inner-sphere ET character of the transition state increases on going from 1-iodobutane and benzyl bromide to benzyl chloride and acetophenone.