Probing organometallic structure and reactivity by transition metal NMR spectroscopy†

Abstract

Transition metal NMR chemical shifts are readily measured by modern 1D and 2D pulse techniques and serve as a probe into electronic and steric effects of ligands and substituents in metal complexes. Quantitative correlations of metal chemical shifts with reaction rates and catalytic activities, both experimental and as a result of quantum chemical calculations, give new mechanistic insights and permit reactivity predictions and a screening of homogeneous catalysts. A variety of such examples involving the spin-1/2 nuclei ⁵⁷Fe, ¹⁰³Rh, and ¹⁸⁷Os as well as the quadrupolar nuclei ⁵¹V, ⁵³Cr, ⁵⁵Mn, ⁵⁹Co, and ⁹¹Zr are discussed.

References

1. D. Rentsch, L. Nill, W. von Philipsborn, D. R. Sidler, P. J. Rybczynski and P. DeShong, Magn. Reson. Chem., 1998, 36, S54.
2. Transition Metal Nuclear Magnetic Resonance, ed. P. S. Pregosin, 1991, Elsevier, Amsterdam.
3. W. von Philipsborn, Pure Appl. Chem., 1986, 58, 513.
4. R. Benn and A. Rufinska, Angew. Chem., Int. Ed. Engl., 1986, 25, 861.
5. E. J. M. Meier, W. Kozminski, A. Linden, P. Lustenberger and W. von Philipsborn, Organometallics, 1996, 15, 2469 and refs. cited therein.
6. D. Rehder, Coord. Chem. Rev., 1991, 110, 161.
7. Multinuclear NMR, ed. J. Mason, 1987, Plenum Press, New York.
8. L. Müller, J. Am. Chem. Soc., 1979, 101, 4481.
9. A. Bax, R. H. Griffey and B. L. Hawkins, J. Am. Chem. Soc., 1983, 105, 7188.
10. R. Benn and C. Brevard, J. Am. Chem. Soc., 1986, 108, 5622.
11. D. Nanz, Indirekte Detektion in der NMR-Spektroskopie metallorganischer Systeme, Konzepte und Anwendungen, PhD Thesis, University of Zürich, 1993.
12. NMR and the Periodic Table, eds. R. K. Harris and B. E. Mann, 1978, Academic Press, London, ch. 3.
13. C. Tavagnacco, G. Balducci, G. Costa, K. Täschler and W. von Philipsborn, Helv. Chim. Acta, 1990, 73, 1469.
14. L. Öhrström, Comments Inorg. Chem., 1996, 18, 305.
15. E. Maurer, S. Rieker, M. Schollbach, A. Schwenk, T. Egolf and W. von Philipsborn, Helv. Chim. Acta, 1982, 65, 26.
16. K. Täschler, Beiträge zur ⁵⁹Co-Kernresonanz metallorganischer Verbindungen, PhD Thesis, University of Zürich, 1990.
17. F. Asaro, G. Costa, R. Dreos, G. Pellizer and W. von Philipsborn, J. Organomet. Chem., 1996, 513, 193.
18. P. S. Pregosin and G. Trabesinger, J. Chem. Soc., Dalton Trans., 1998, 727.
19. H. Bönnemann, W. Brijoux, R. Brinkmann, W. Meurers, R. Mynott, W. von Philipsborn and T. Egolf, J. Organomet. Chem., 1984, 272, 231.
20. H. Bönnemann, Angew. Chem., Int. Ed. Engl., 1985, 24, 248.
21. C. Marzin, F. Budde, P. J. Steel and D. Lerner, Nouv. J. Chim., 1987, 11, 33.
22. P. DeShong, D. R. Sidler, P. J. Rybczynski, A. A. Ogilvie and W. von Philipsborn, J. Org. Chem., 1989, 54, 5432.
23. M. Koller and W. von Philipsborn, Organometallics, 1992, 11, 467.
24. V. Tedesco and W. von Philipsborn, Organometallics, 1995, 14, 3600.
25. M. Cheong and F. Basolo, Organometallics, 1988, 7, 2041.
26. G. Cardaci, Int. J. Chem. Kinet., 1973, 5, 805.
27. M. Koller, CO-Austauschreaktionen an Metallcarbonyl(Olefin)-Komplexen', PhD Thesis, University of Zürich, 1993.
28. K. Angermund, W. Baumann, E. Dinjus, R. Fornika, H. Görls, M. Kessler, C. Krüger, W. Leitner and F. Lutz, Chem. Eur. J., 1997, 3, 755.
29. C. R. Landis and J. Halpern, J. Am. Chem. Soc., 1987, 109, 1746 and refs. cited therein.
30. B. R. Bender, M. Koller, D. Nanz and W. von Philipsborn, J. Am. Chem. Soc., 1993, 115, 5889.
31. A. Hafner, L. S. Hegedus, G. de Weck, B. Hawkins and K. H. Dötz, J. Am. Chem. Soc., 1988, 110, 8413.
32. A. Hafner, R. O. Duthaler, R. Marti, G. Rihs, P. Rothe-Streit and F. Schwarzenbach, J. Am. Chem. Soc., 1992, 114, 2321.
33. M. Bühl, G. Hopp, W. von Philipsborn, S. Beck, M.-H. Prosenc, U. Rief and H.-H. Brintzinger, Organometallics, 1996, 15, 778.
34. A. G. Bell, W. Kozminski, A. Linden and W. von Philipsborn, Organometallics, 1996, 15, 3124.
35. M. Bühl and F. A. Hamprecht, J. Comput. Chem., 1998, 19, 113 and refs. cited therein.
36. M. Bühl, Habilitationsschrift, University of Zürich, 1997, and refs. cited therein.
37. M. Bühl, Angew. Chem., Int. Ed. Engl., 1998, 37, 142.
38. I. P. Gerothanassis, C. G. Kalodimos, G. Hawkes and P. Haycock, J. Magn. Reson., 1998, 131, 163 and refs. cited therein.
39. D. Rentsch, R. Hany and W. von Philipsborn, Magn. Reson Chem., 1997, 35, 832 and refs. cited therein.