(Hg) Mercury NMR

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

Chemical shifts of mercury

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 spectrum

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

199Hg spectrum coupled to proton

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

1H spectrum coupled to 199Hg

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

199Hg spectrum coupled to 13C

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

13C spectrum coupled to 199Hg

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Properties of 199Hg

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Natural abundance16.87%
Chemical shift range3500 ppm, from -3000 to 500
Frequency ratio (Ξ)17.910822%
Reference compoundMe2Hg (neat)
Linewidth of reference2.6 Hz
T1 of reference0.5 s
Receptivity rel. to 1H at natural abundance1.00 × 10-3
Receptivity rel. to 1H when enriched5.93 × 10-3
Receptivity rel. to 13C at natural abundance5.89
Receptivity rel. to 13C when enriched34.9

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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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Natural abundance13.18%
Chemical shift range3500 ppm, from -3000 to 500
Frequency ratio (Ξ)6.611583%
Reference compoundMe2Hg (neat)
Linewidth of reference>40000 Hz
T1 of reference<0.00002 s
Receptivity rel. to 1H at natural abundance1.97 × 10-4
Receptivity rel. to 1H when enriched1.49 × 10-3
Receptivity rel. to 13C at natural abundance1.16
Receptivity rel. to 13C when enriched8.80
Linewidth parameter2000 fm4

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