(Hg) Mercury NMR

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shailendra Mercury Our NMR service

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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 (LD Me Hg, 0.1 mL!): wear protective clothing and work in a hood.
50 2

Hg
199

Properties of
201

Hg

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.

Hg
201

Properties of Hg References 1D NMR NMR techniques Back to home page

Mercury (Hg) has two NMR active nuclei, very wide chemical shift range.
199 201

199

Hg and

201

Hg.

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Hg is a low sensitivity spin- nucleus that yields sharp signals over a

199

Hg a quadrupolar low sensitivity nucleus that yields signals too broad to be observed with a Hg is the mercury nucleus of

high-resolution NMR spectrometer even for small molecules such as dimethyl mercury. Therefore,

choice. Hg-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

199
199

Hg yields sharp signals (fig. 2) and is more sensitive than

201

Hg. Therefore

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Hg is the mercury nucleus of choice.

Fig. 2.

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Hg-NMR, proton decoupled, of Me Hg (neat)

2

199 13

Hg couples with many nuclei. Two-bond H-

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Hg couplings are between 100 and 270 Hz (figs. 3 and 4). One-bond couplings to

C 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.

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Hg-NMR of Me Hg (neat) showing proton coupling

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Fig. 4. H-NMR of Me Hg (neat) showing coupling to

2

199

Hg

Fig. 5.

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Hg-NMR of Me Hg (neat) showing coupling to

2

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Fig. 6.

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C-NMR of Me Hg (neat) showing coupling to

2

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Hg

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(Click here for explanation) Property Spin Natural abundance Chemical shift range Frequency ratio () Reference compound Linewidth of reference T of reference
1

Value 1/2 16.87% 3500 ppm, from -3000 to 500 17.910822% Me Hg (neat)
2

2.6 Hz 0.5 s 1.00 10 5.93 10 5.89 34.9

-3 -3

Receptivity rel. to H at natural abundance Receptivity rel. to H when enriched Receptivity rel. to Receptivity rel. to Back to top of page
13 13 1

C at natural abundance C when enriched

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201
201

Hg is a quadrupolar nucleus that yields signals too broad cannot be observed on a high resolution NMR spectrometer even for
201 2

small molecules such as Me Hg.

Hg is also less sensitive than

199

Hg. Therefore,

201

Hg is not the mercury nucleus of choice for

NMR. Because it is unobservable, we have no useful experience of Back to top of page

201

Hg-NMR in our laboratory.

201
(Click here for explanation) Property Spin Natural abundance Chemical shift range Frequency ratio () Reference compound Linewidth of reference T of reference
1

Value 3/2 13.18% 3500 ppm, from -3000 to 500 6.611583% Me Hg (neat)
2

>40000 Hz <0.00002 s 1.97 10 1.49 10 1.16 8.80 2000 fm

4 -4 -3

Receptivity rel. to H at natural abundance Receptivity rel. to H when enriched Receptivity rel. to
13 13 1

C at natural abundance

Receptivity rel. to C when enriched Linewidth parameter Back to top of page

1. V. S. Petrosyan, and O. A. Reutov, "Study of the structure and complexation of organic and inorganic derivatives of metals by means of NMR spectroscopy of heavy nuclei", Pure Appl. Chem., 37, 147-59 (1974). 2. M. Borzo and G. E. Maciel, "Mercury-199 chemical shifts of organomercury compounds by Fourier transform NMR", J. Magn. Reson., 19, 279-282 (1975). 3. N. K. Wilson, R. D. Zehr and P. D. Ellis, "Carbon-13 nuclear magnetic resonance. Carbon-13 chemical shifts and carbon13-mercury-199 coupling constants for some organomercury compounds", J. Magn. Reson., 21, 437-443 (1976). 4. J. L. Sudmeier and T. G. Perkins, " Studies of single HgII ion resonances in the active site of human carbonic anhydrase B by Fourier transform nuclear magnetic resonance", J. Am. Chem. Soc., 99, 7732-7733 (1977). 5. A. J. Canty, A. Marker, P. Barron and P. C. Healy, "A mercury-199 NMR spectroscopic study of two- and three-coordinate methylmercury(II) complexes, [MeHgL]NO ", J. Organometal. Chem., 144, 371-379 (1978).
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6. Y. A. Strelenko, Y. G. Bundel, F. H. Kasumov, V. I. Rozenberg, O. A. Reutov and Y. A. Ustynyuk, ",,-Conjugation and mercury-199 shielding constants in benzyl derivatives of mercury", J. Organometal. Chem., 159, 131-135 (1978). 7. M. J. Albright and J. P. Oliver, "Studies on main group metal-transition-metal bonded compounds. 7. A mercury-199 NMR study of some Group VI transition-metal mercury compounds", J. Organometal. Chem., 172, 99-107 (1979). 8. R. Colton and D. Dakternieks, "Phosphorus-31 and mercury-199 NMR studies on mercury (II) halide-tributylphosphine complexes", Aust. J. Chem., 33, 955-963 (1980). 9. R. Meyer, L. Gorrichon-Guigon and P. Maroni, "Carbon-13 and mercury-199 NMR study on oxobromo- and dioxomercuric compounds", J. Organometal. Chem., 188, 11-24 (1980). 10. M. F. Roberts, D. A. Vidusek and G. Bodenhausen, "Adducts of ethylmercury phosphate with amino acids studied by indirect detection of mercury-199 NMR", FEBS Lett., 117, 311-314 (1980). 11. P. R. Wells and D. W. Hawker, "Mercury-199 NMR chemical shifts in substituted diphenylmercury and phenylmercuric chloride", Org. Magn. Reson., 17, 26-27 (1981). 12. M. J. Albright, T. F. Schaaf, A. K. Hovland and J. P. Oliver, "Metal-silicon bonded compounds. XVIII. A mercury-199 FT NMR study of some silylmercury derivatives and selected organomercury compounds", J. Organometal. Chem., 259, 37-50 (1983). 13. A. M. Bond, R. Colton, M. L. Dillon, J. E. Moir and D. R. Page, "Investigation of exchange and redox reactions of mercury dithiocarbamate complexes by electrochemical techniques at mercury electrodes, mercury-199 nuclear magnetic resonance spectrometry and mass spectrometry", Inorg. Chem., 23, 2883-2889 (1984). 14. A. R. Norris and R. Kumar, "Mercury-199 NMR correlations in methylmercury(II) complexes of nucleic acid constituents and their analogs", Inorg. Chim. Acta, 93, L63-L65 (1984). 15. P. A. W. Dean and R. S. Srivastava, "A multinuclear (proton, phosphorus-31, mercury-199) nuclear magnetic resonance study of some complexes of mercury (II) with ditertiary phosphines", Can. J. Chem., 63, 2829-2839 (1985). 16. K. E. Rowland and R. D. Thomas, "Carbon-13 and mercury-199 NMR data for methyl-substituted diarylmercury compounds", Magn. Reson. Chem., 23, 916-919 (1985). 17. G. B. Deacon, M. J. O'Connor and G. N. Stretton, "Organomercury compounds. XXVIII. The synthesis and mercury-199 NMR spectra of some unsymmetrically dimercurated arenes", Aust. J. Chem., 39, 953-962 (1986). 18. B. F. Abrahams, M. Corbett, D. Dakternieks, R. W. Gable, B. F. Hoskins, E. R. T. Tiekink and G. Winter, "NMR studies of phosphine adducts of mercury and cadmium xanthates and halo xanthates. Crystal and molecular structures of Cd(S COPr2

iso) PPh , Hg(S COPr-iso) PPh and Hg(S COPr-iso) P(c-C H ) (c-C H
2 3 2 2 3 2 2 6 11 3

6 11

= cyclohexyl)", Aust. J. Chem., 39, 1993-2001

(1986). 19. L. V. Pankratov, I. M. Penyagina, L. N. Zakharov, M. N. Bochkarev, G. A. Razuvaev, Y. K. Grishin, Y. A. Ustynyuk and Y. T. Struchkov, "Reactivity of germylmercurate complexes", J. Organometal. Chem., 335, 313-322 (1987). Hg NMR studies on complexes 20. M. M. Kubicki, J. Y. Le Gall, R. Pichon, J. Y. Salaun, M. Cano and J. A. Campo, " Mo and containing molybdenum-mercury bonds and substituted cyclopentadienyl ligands: [(C H -nR )(CO) Mo]xHgX (R = Me, n =
5 5 n 3 2-x 95 199

0, 1, 4, 5; R = Ph, n = 4; X = Cl, Br, I; x = 1, 2)", J. Organometal. Chem., 348, 349-356 (1988). 21. M. Delnomdedieu, D. Georgescauld, A. Boudou and E. J. Dufourc, "Mercury-199 NMR. A tool to follow chemical speciation of

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mercury compounds", Bull. Magn. Reson., 11, 420 (1989). 22. M. Delnomdedieu, A. Boudou, D. Georgescauld and E. J. Dufourc, "Specific interactions of mercury chloride with membranes and other ligands as revealed by mercury NMR", Chem. Bio. Interact., 81, 243-269 (1992). 23. M. Cano, J. A. Campo, J. Y. Le Gall, R. Pichon, J. Y. Salaun and M. M. Kubicki, "Molybdenum- mercury bond. NMR (mercury-199, phosphorus-31, proton) and IR study on [(C H )(CO) LMoHgZ] [L = P(4-XC H ) (X = F, Cl, Me, OMe),
5 5 2 6 4 3

P(CH CH ) , P(CH CH CN) ; Z = Cl, I, (C H )(CO) LMo] complexes", Inorg. Chim. Acta, 193, 207-212 (1992).
2 3 3 2 2 3 5 5 2

24. L. Yang, J. Chen, X. Lei, Y. Wu and M. Song, "Substituent effect on mercury-199 chemical shifts in some bisarylmercurials and aryl(2-benzothiazolylthio)mercurials", 25. Chem. Res. Chin. Univ. , 8, 81-83 (1992). 26. X. Yang, Z. Zheng, C. B. Knobler and M. F. Hawthorne, ""Anti-crown" chemistry: synthesis of [9]mercuracarborand-3 and the crystal structure of its acetonitrile complexes", J. Am. Chem. Soc., 115, 193-195 (1993). 27. Y. K. Grishin, V. V. Orlov, G. A. Artamkina and Y. A. Ustynyuk, "Mercury-199 nuclear magnetic shielding constants of benzyl mercury derivatives", Zh. Organich. Khim., 30, 1601-1607 (1994). 28. Y. J. Wu, S. Q. Huo, H. Z. Yuan and Y. H. Liu, "Secondary interaction and n- conjugation in ferrocenylimine derivatives of mercury as probed by Hg-199 NMR", Main Group Chem., 1, 253-256 (1996). 29. A. Berra, M. L. Di Vona, B. Floris and S. Licoccia, " Hg NMR: a tool for direct detection of the products from acetoxymercuration of alkynes", Appl. Organometal. Chem., 14, 565-569 (2000). 30. F. S. H. Vieco, N. M. Hiramatsu, E. Tedeschi, D. B. Rezende and I. P. A. Campos, "The -cis effect in the mercury-199 NMR spectroscopy of substituted vinylmercury halides", J. Chem. Res., Syn., 25-27 (2002). Back to top of page
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Mercury, Use our NMR service,
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Hg, Properties of

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Hg,

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Hg, Properties of

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Hg, References, 1D NMR, NMR techniques, Back to home page

Roy Hoffman and Yair Ozery, The Hebrew University, Revised 2011-08-01T11:20+03

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