Journal of the Chemical Society, Dalton Transactions p. 637 - 640 (1990)
Update date:2022-08-16
Topics:
Hasegawa, Akinori
Rideout, Jan
Symons, Martyn C.R.
Exposure of very dilute solutions of Hg(CD3)2 in tetrachloromethane to 60Co γ-rays at 77 K gave a species whose e.s.r. spectrum is characteristic of the parent cation.Interpretation of the g-values and 199Hg tensor component B derived from a computer synthesis of the spectrum suggests that the unpaired electron is strongly confined to the linear ? orbital having a node through the mercury atom.This has a large 6p(Hg) character.No extra features were obtained using Hg(13CH3)(CH3), confirming that the spin density on the CH3 groups is small (<20percent).When CFCl3 was the solvent extra poorly defined splittings were observed which are assigned to weak, but specific interaction with one solvent molecule (19F).The spectra for Hg(CH3)2 in this solvent were analysed in terms of the same solvent features together with coupling to a least five and probably seven protons.The small 1H coupling was almost isotropic at +/-4.5 G.In contrast, Hg(C2H5)2 gave no resolved coupling to 19F, but there was a large, well defined, triplet splitting (42 G) assigned to two specific CH3 protons.This suggests that rotation about the C-C bonds is restricted.We were unable to detect free rotation on annealing, although the lines broadened considerably, prior to radical loss.Attempts to detect .CH3 or .CH2CH3 radicals in these systems were unsuccessful, but clear evidence for .CD3 radicals was obtained for Hg(CD3)2 in CFCl3 on annealing.
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