Bulletin of the Korean Chemical Society

Korean Chemical Society (대한화학회)
권호 표지
DOI QR코드

DOI QR Code

Ab initio Nuclear Shielding Calculations for Some X-Substituted Silatranes Using Gauge-Including Atomic Orbitals

  • Published : 1997.09.20
Download PDF
⟨ Previous Next ⟩

Abstract

13C, 15N, and 29Si NMR chemical shifts have been computed for selected X-substituted silatranes (X=Cl, F, H, CH3) using Gauge-Including Atomic Orbitals (GIAO) at the Hartree-Fock level of theory. The isotropic 13C chemical shifts are largely insensitive to substituent-induced structural changes. In this study, the isotropic 13C chemical shifts between 1-methyl- and 1-hydrogensilatranes by GIAO-SCF calculation at the HF/6-31G level are very similar. But the results of 1-chloro- and 1-fluorosilatranes are about 4 ppm different from the experimental values. In contrast, the isotropic 15N and 29Si chemical shifts and the chemical shielding tensors are quite sensitive to substituent-induced structural changes. These trends are consistent with those of the experiment. The isotropic 15N chemical shift demonstrates a very clear correlation with Si-N distance. But in case of 29Si the correlations are not as clean as for the 15N chemical shift; the calculated variation in the 29Si chemical shift is much larger.

Keywords

References

  1. Pure Appl. Chem. v.13 Voronkov, M. G.
  2. J. Organomet. Chem. v.233 Voronkov, M. G.;Dyakov, V. M.;Kirpichenko, S. V.
  3. Rev. Silicon, Germanium, Tin Lead Compd. v.8 Hencsei, P.;Parkanyi, L.
  4. J. Organoment. Chem. v.1 Parkanyi, L.;Hencsei, P.;Bihatsi, L.;Muller, T.
  5. Struct. Chem. v.1 Forgacs, G.;Kolonits, M.;Hargittai, I.
  6. Cryst. Sturct. Commum. v.7 Parkanyi, L.;Bihatsi, L.;Hencsei, P.
  7. J. Mol. Struct. v.64 Shen, Q.;Hilderbrandt, R. L.
  8. Dokl. Akad. Nauk SSSR v.243 Kemme, A. A.;Bleidelis, Ya.;Pestunovich, V. A.;Baryshok, V. P.;Voronkov, M. G.
  9. The Nature of the Chemical Bond Pauling, L.
  10. Inorg. Chim. Acta v.20 Glidewell, C.
  11. Dokl. Akad. Nauk SSSR v.301 Sidurkin, V. F.;Balakchi, G. K.;Voronkov, M. G.;Pestunovich, V. A.
  12. Mol. Phys. v.27 Ditchfield, R.
  13. Chem. Phys. Lett. v.154 TURBOMOLE and TURBONMR are commercially a vailable from MSI TURBOMOLE: Ahlrichs, R.;Bar, M.;Haser, M.;Horn, H.;Kolmel, C.
  14. Magn. Reson. Chem. v.24 Bellama, J. M.;Nice, J. D.;Ben-Zvi, N.
  15. J. Magn. Reson. v.30 Harris, R. K.;Jones, J.;Ng, S.
  16. J. Am. Chem. Soc. v.115 Iwamiya, J. H.;Maciel, G. E.
  17. Magn. Res. Rev. v.11 Fukui, H.
  18. Annual Reports on NMR Spectroscopy v.21 Chesnut, D. B.;Webb, G. A.(Ed)
  19. Dokl. Akad. Nauk SSSR v.258 Pestunovich, V. A.;Shterenberg, B. Z.;Lippmaa, E. T.;Myagi, M. Ya.;Alla, M. A.;Tandura, S. N.;Baryshok, V. P.;Petukhov, L. P.;Voronkov, M. G.
  20. J. Comput. Chem. v.15 Csonka, G. I.;Hencsei, P.
  21. J. Comput. Chem. v.17 Csonka, G. I.;Hencsei, P.
  22. J. Chem. Phys. v.99 Gauss, J.
  23. J. Am. Chem. Soc. v.118 Olah, G. A.;Rasul, G.;Heiliger, L.;Prakash;G. K. S.
  24. J. Phys. Chem. v.100 Rauhut, G.;Puyear, K. W.;Pulay, P.
  25. J. Phys. Chem. v.99 Schreckenbach, G.;Ziegler, T.