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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, selenium compounds are toxic or very toxic, work in a hood and use appropriate gloves and protective clothing. Latex gloves are insufficient protection against organoselenium compounds.
Se
77
77
Selenium ( Se) is a low sensitivity spin nucleus that yields narrow lines over a very wide chemical shift range. Each type of selenium compound has its characteristic chemical shift range (fig. 1).
77 77
Selenium NMR (fig. 2) is used extensively in the study of organoselenium compounds such as selenoxanthenone (fig. 3) and for studies of selenium binding to proteins.
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Selenium often shows couplings to other nuclei, H, C, N, F, P, etc. It also displays homonuclear couplings with three-bond selenium-selenium couplings between 10 and 100 Hz that depend on stereochemistry. Selenium couplings to protons can be removed by decoupling as in fig. 2. The coupled spectrum of selenoxanthenone (fig. 4) shows a three bond coupling to H1 ( J of 11.6 Hz, four bond coupling to H2 ( J
4 Se,H 3 Se,H
13
15
19
31
Se,H
Fig. 4.
77
coupling
The selenium couplings are also observed as satellites in the proton spectrum (fig. 5). They only appear as satellites because the abundance of
77
Se is only 7.63%.
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Se
coupling
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C coupling is manifested as small satellite signals in the Se spectrum (fig. 6). Here couplings up to three bonds are observed. One bond coupling constants are in the region of 100 Hz, 2 and 3 bond couplings range from 5 to 35 Hz and longer range couplings are less than 3 Hz.
13
77
77
C coupling
13
13
Se coupling
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(Click here for explanation)
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Property Spin Natural abundance Chemical shift range Frequency ratio () Reference compound Linewidth of reference T of reference
1
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
1. M. Lardon, "Selenium and proton nuclear magnetic resonance measurements on organic selenium compounds", J. Am. Chem. Soc., 92, 5063-5066 (1970). 2. W. McFarlane and D. S. Rycroft, "Signs of nuclear spin-spin coupling constants involving selenium. Effect of electron lone pairs", J. Chem. Soc. Chem. Commun., 10-11 (1973). 3. S. Gronowitz, I. Johnson and A. B. Hornfeldt, "Selenium-77 NMR studies of organoselenium compounds. I. Selenium-77 NMR parameters of monosubstituted selenophenes", Chem. Script., 8, 8-14 (1975). 4. L. Christiaens, J. L. Piette, L. Laitem, M. Baiwir, J. Denoel and G. Llabres, "Selenium-77 NMR of organoselenium compounds", Org. Magn. Reson., 8, 354-356 (1976). 5. A. Fredga, S. Gronowitz and A. B. Hornfeldt, "Selenium-77 NMR studies of organoselenium compounds. IV. Benzyl- and arylseneinic acids", Chem. Script., 11, 37-38 (1977). 6. G. A. Kalabin, D. F. Kushnarev and V. M. Tschmutova, "Proton, carbon-13, and selenium-77 NMR spectra of substituted selenoanisoles", Org. Magn. Reson., 12, 598-604 (1979). 7. R. Keat, D. S. Rycroft and D. G. Thompson, "Selenium-77 chemical shifts of cylodiphosphazene selenides", Org. Magn. Reson., 12, 391-392 (1979). 8. B. Kohne, W. Lohner, K. Praefcke, H. J. Jakobsen and B. Villadsen, "Spectroscopic investigations XVII. Se and Te NMR resonances of some selenol and tellurol esters", J. Organometal. Chem., 166, 373-377 (1979). 9. G. Llabres, M. Baiwir, J. L. Piette and L. Christiaens, "Selenium-77, carbon-13 and proton NMR investiagation on orthocarbonyl benzeneselenyl derivatives", Org. Magn. Reson., 15, 152-154 (1981). 10. N. V. Onyamboko, M. Renson, S. Chapelle and P. Granger, "Carbon-13 and Selenium-77 spectra of thienoisoselenazoles, selenoloisothiazoles, selnoloisoselnazoles, and thienoisothiazoles", Org. Magn. Reson., 19, 74-77 (1982). 11. D. F. Kushnarev, G. A. Kalabin, R. A. Kyandzhetsian and N. N. Magdesieva, "NMR spectroscopy of organic compounds of selenium and tellurium. X. Chemical shifts of selenium-77 in selenonium ylides", Zh, Org. Khim., 18, 119-124 (1982). 12. M. Baiwir, G. Llabres, L. Christiaens and J. L. Piette, "NMR studies of the chalcogen analogs of benzofuran. IV. Proton, carbon-13 and selenium-77 magnetic resonance in nitrobenzo[b]selenophenes", Org. Magn. Reson., 18, 33-37 (1982). 13. N. P. Luthram R. B. Dunlap and J. D. Odom "Selenium-77 NMR studies of organic selenyl sulfides", J. Magn. Reson., 46, 152-157 (1982). 14. I. Johannsen and H. Eggert, "Selenium-77 NMR. Observation of J
77 3 Se-Se 77 125
substituted tertaselenfulvalenses", J. Am. Chem. Soc., 106, 1240-1243 (1984). 15. H. Duddeck, P. Wagner and S. Gegner, "Dynamic Se NMR of phenylselenyl cyclohexane derivatives", Tetrahed. Lett., 26, 1205-1208 (1985). 16. H. Eggert, O. Nielson and L. Henriksen, "Selenium-77 NMR. Application of J to the analysis of dialkyl selenides", J. Am.
Se-Se
Chem. Soc., 108, 1725-1730 (1986). 17. I. Johannsen, L. Henrikson and H. Eggert, "Selenium-77 NMR. 2. The basis for application of J
Se-Se
and J
Se-H
in structure
assignments of mono-, di-, and triseleno-substituted alkenes", J. Org. Chem., 51, 1657-1663 (1986). 18. K. S. Tan, A. P. Arnold and D. L. Rabenstein, "Selenium-77 nuclear magnetic resonance studies of selenols, diselenides, and selenyl sulfides", Can. J. Chem., 66, 54-60 (1988). 19. B. Wrackmeyer, B. Distler, S. Gerstmann and M. Herberhold, "Nitrogen-15 and Selenium-77 nuclear magnetic resonance study of selenium diimides and aminoselenanes", Z. Naturfors. B, 48, 1307-14 (1993). 20. B. W. Tattershall and E. L. Sandham, "Interdependence of phosphorus-31 selenium-77 NMR coupling constants in bicyclic phosphorus selenide compounds", J. Chem. Soc. Dalton Trans., 1834-1840 (2001). Back to top of page
Se, Properties of
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Roy Hoffman and Yair Ozery, The Hebrew University, Revised 2011-06-22T15:24+03
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