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, tungsten salts are toxic: wear protective gloves.

¹⁸³W NMR

Tungsten (W) has one very low sensitivity NMR active nucleus, ¹⁸³W (fig. 1). It is a spin ½ nucleus and yields sharp signals over a very wide chemical shift range. ¹⁸³Tungsten NMR is mostly used for studying tungsten complexes, especially polyoxide clusters.

Fig. 1. ¹⁸³W-NMR spectrum of Na₂WO₄ (1 M) in D₂O

Each type of tungsten its representative chemical shift range (fig. 2).

Fig. 2. Chemical shift ranges for tungsten NMR

Tungsten shows couplings with other nuclei. One-bond couplings with fluorine are between 20 and 70 Hz. One-bond couplings to ³¹P are of the order of 250 Hz. With ⁵¹V, two-bond couplings of up to 26 Hz are observed. Couplings are also reported with ¹⁰B, ¹¹B and ²⁹Si. In polytungstates, homonuclear couplings (two-bond between 5 and 30 Hz) appear as satellite signals in the tungsten spectrum allowing the use of 2D-INADEQUATE for spectral assignment as with ¹³C-NMR.

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Properties of ¹⁸³W

(Click here for explanation)

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References

1. W. McFarlane, A. M. Noble and J. M Winfield, "Reversal of the sign of the tungsten-183-fluorine-19 spin-spin coupling constant in octahedral tungsten (VI) derivatives" Chem. Phys. Lett., 6, 547-548 (1970).
2. F. H. Koehler, H. J. Kalder and E. O. Fischer, "Carbon-13-tungsten-183 coupling as a probe for metal-carbyne, -carbene, and -alkyl compounds", J. Organometal. Chem., 85, C19-C22 (1975).
3. J. Banck and A. Schwenk, "Tungsten-183 NMR studies", Z. Phys. B, 20, 75-80 (1975).
4. R. Acerete, C. F. Hammer and L. C. W. Baker, "Direct tungsten-183 nuclear magnetic resonance: a powerful new structural tool for heteropoly- and isopolytungstate chemistry", J. Am. Chem. Soc., 101, 267-269 (1979).
5. M. A. Fedotov, L. P. Kazanskii and V. I. Spitsyn, "Oxygen-17 and tungsten-183 NMR chemical shifts in polyoxotungstates and the lengths of tungsten -oxygen bonds", Dokl. Akad. Nauk SSSR, 272, 1179-1185 (1983).
6. P. J. Domaille, "The 1- and 2-dimensional tungsten-183 and vanadium-51 NMR characterization of isopolymetalates and heteropolymetalates", J. Am. Chem. Soc., 106, 7677-7687 (1984).
7. Y. Ma, P. Demou and J. W. Faller, "A tungsten-183 NMR study of mononuclear tungsten (VI) methyl complexes containing terminal oxo, sulfido, and imido ligands", Inorg. Chem., 30, 62-64 (1991).
8. J.-F. Liu, W.-Q. Wang, L. Meng and Y. Liu, "¹⁸³W NMR characterization of rare earth heteropolymetalates in aqueous solution", Gaodeng Xuexiao Huaxue Xuebao, 17, 179-182 (1996).
9. L. Zhang, M. P. Gamasa, J. Gimeno, R. J. Carbajo, F. Lopez-Ortiz, M. Lanfranchi and A. Tiripicchio, "Synthesis and Characterization of Tungsten Alkenyl-Carbyne Complexes [cyclic] trans-[(dppe)(CO)₂LW≡CCH:CCH₂(CH₂)_nCH₂CH₂][BF₄] (L = CO, MeCN, PMe₃) and [cyclic] [(dppe)(CO)₂XW≡CCH:CCH₂(CH₂)_nCH₂CH₂] (X = Cl, Br, I). X-ray Crystal Structure of [(dppe)(CO)₂ClW≡CCH:CCH₂CH₂)_nCH₂CH₂] and ¹⁸³W NMR Studies", Organometal., 15, 4274-4284 (1996).
10. S. Chapelle, P. Koll, Peter and J.-F. Verchere, "A multinuclear NMR spectroscopy characterization of dinuclear tungsten (VI) complexes of tridentate and pentadentate meso-D-glycero-D-gulo-heptitol and D-glycero-L-gulo-heptitol", Carbohydr. Res., 306, 27-34 (1998).
11. R. J. Carbajo, L. Zhang, Lei and F. Lopez-Ortiz, "¹⁸³W NMR study of alkenylcarbyne- and alkenylvinylidene- tungsten complexes", Magn. Reson. Chem., 36, 807-814 (1998).
12. Y. Chen, L. Qu, Lunyu and J. He, "Application of ¹⁸³W NMR technique in the study of polyoxometalates", Huaxue Tongbao, 65, w53/1-w53/6 (2002).
13. B. J. Smith and V. A. Patrick, "Tungsten NMR spectra of the α- and β-isomers of Na₈[SiW₁₁O₃₉]", Aust. J. Chem., 56, 283-286 (2003).
14. I. Kawafune, "¹⁸³W NMR spectral behavior of A-type metal-trisubstituted dodecatungstophosphate anion salts", Kagaku to Kogyo, 77, 452-458 (2003).
15. G. Lenoble, B. Hasenknopf and R. Thouvenot, "A Strategy for the Analysis of Chiral Polyoxotungstates by Multinuclear (³¹P, ¹⁸³W) NMR Spectroscopy Applied to the Assignment of the ¹⁸³W NMR Spectra of a 1-[P₂W₁₇O₆₁]^10- and a 1-[YbP₂W₁₇O₆₁]^7-", J. Am. Chem. Soc., 128, 5735-5744 (2006).

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