Safety note: Some of the materials mentioned here are very dangerous. Ask a qualified chemist for advice before handling them. Qualified chemists should check the relevant safety literature before handling or giving advice about unfamiliar substances. NMR solvents are toxic and most are flammable. Specifically, mercury salts are very toxic: wear protective gloves and work in a hood. Dimethyl mercury and other organomercuries are very toxic (LD₅₀ Me₂Hg, 0.1 mL!): wear protective clothing and work in a hood. Latex gloves do not provide protection. Highly resistant laminate gloves (SilverShield or 4H) should be worn under a pair of long-cuffed, unsupported neoprene, nitrile, or similar heavy-duty gloves. One drop can kill.

Mercury NMR

Mercury (Hg) has two NMR active nuclei, ¹⁹⁹Hg and ²⁰¹Hg. ¹⁹⁹Hg is a low sensitivity spin-½ nucleus that yields sharp signals over a very wide chemical shift range. ²⁰¹Hg a quadrupolar low sensitivity nucleus that yields signals too broad to be observed with a high-resolution NMR spectrometer even for small molecules such as dimethyl mercury. Therefore, ¹⁹⁹Hg is the mercury nucleus of choice. ¹⁹⁹Hg-NMR is used for the study of mercury compounds, their structure, dynamics and conformation. It is also used for biological binding studies using its relaxation effects.

Each type of mercury compound has its characteristic chemical shift range (fig. 1).

Fig. 1. Chemical shift ranges for mercury NMR

¹⁹⁹Mercury NMR

¹⁹⁹Hg yields sharp signals (fig. 2) and is more sensitive than ²⁰¹Hg. Therefore ¹⁹⁹Hg is the mercury nucleus of choice.

Fig. 2. ¹⁹⁹Hg-NMR, proton decoupled, of Me₂Hg (neat)

¹⁹⁹Hg couples with many nuclei. Two-bond ¹H-¹⁹⁹Hg couplings are between 100 and 270 Hz (figs. 3 and 4). One-bond couplings to ¹³C are between 600 and 3000 Hz (figs. 5 and 6), two-bond from 70 to 130 Hz and three-bond 100 to 220 Hz.

Fig. 3. ¹⁹⁹Hg-NMR of Me₂Hg (neat) showing proton coupling

Fig. 4. ¹H-NMR of Me₂Hg (neat) showing coupling to ¹⁹⁹Hg

Fig. 5. ¹⁹⁹Hg-NMR of Me₂Hg (neat) showing coupling to ¹³C

Fig. 6. ¹³C-NMR of Me₂Hg (neat) showing coupling to ¹⁹⁹Hg

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Properties of ¹⁹⁹Hg

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²⁰¹Mercury NMR

²⁰¹Hg is a quadrupolar nucleus that yields signals too broad cannot be observed on a high resolution NMR spectrometer even for small molecules such as Me₂Hg. ²⁰¹Hg is also less sensitive than ¹⁹⁹Hg. Therefore, ²⁰¹Hg is not the mercury nucleus of choice for NMR. Because it is unobservable, we have no useful experience of ²⁰¹Hg-NMR in our laboratory.

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Properties of ²⁰¹Hg

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