On the factors to determine 77Se NMR chemical shifts of organic selenium compounds: Application of GIAO magnetic schielding tensor to the 77Se NMR spectroscopy

Chemistry Letters

Volumn , Issue 6, 1998, Pages 523-524

  Nakanishi, Waro ^a   Hayashi, Satoko ^a  

^a WAKAYAMA UNIVERSITY   (Japan)

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EID: 0032380841     PISSN: 03667022     EISSN: None     Source Type: Journal    
DOI: 10.1246/cl.1998.523     Document Type: Article

References (23)

1. -3> factor of the 4p orbitals is expected to be proportional to the atomic charge on the Se atom being observed. The ΔE factor, the average excitation energy, could be estimated by the energy difference between HOMO and LUMO of the compound if the 4p atomic orbitals of the selenium atom substantially contribute to both of the orbitals. The HOMO of 6 and 7 of the A″ symmetry are mainly constructed by the p-type lone pair of the Se atom. The situation is similar for LUMO of 6 (the A″ symmetry). The p-type orbital also contributes to LUMO of 7 with the A′ symmetry, which bisects its CSeH angle.
2. 77Se NMR Chemical Shifts," Wiley, New York (1996).
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5. W. Nakanishi, S. Hayashi, and H. Yamaguchi, Chem. Lett. 1996, 947. δ(Se)of 1 = 1.33 × δ(Se) of 2 - 147.1 (r = 0.994) (b)
6. a) W. Nakanishi, S. Hayashi, and S. Toyata, J. Chem. Soc., Chem. Commun., 1996, 371.
7. b) W. Nakanishi, S. Hayashi, and S. Toyata, unpublished results.
8. 3. See, G. A. Kalabin, D. F. Kushnarev, V. M. Bzesovsky, and G. A. Tschmutova, Org. Mag. Res., 12, 598 (1979).
9. The correlations of δ(Se) in 1 and 2 with those of 4 are as follows: δ(Se) of 1 = 1.07 × δ(Se) of 4 - 21.4 (r = 0.996) (c) δ(Se) of 2 =0.79 × δ(Se) of 4 + 98.2 (r = 0.991) (d).
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13. J. R. Cheeseman, G. W. Trucks, T. A. Keith, and M. J. Frisch, J. Chem. Phys., 104, 5497 (1996). See also, D. A. Forsyth and A. B. Sebag, J. Am. Chem. Soc. 119, 9483 (1997); G. A. Olah, T. Shamma, A. Burrichter, G. Rasul, and G. K. S. Prakash, J. Am. Chem. Soc., 119, 12923, 12929 (1997).
14. J. R. Cheeseman, G. W. Trucks, T. A. Keith, and M. J. Frisch, J. Chem. Phys., 104, 5497 (1996). See also, D. A. Forsyth and A. B. Sebag, J. Am. Chem. Soc. 119, 9483 (1997); G. A. Olah, T. Shamma, A. Burrichter, G. Rasul, and G. K. S. Prakash, J. Am. Chem. Soc., 119, 12923, 12929 (1997).
15. S. Tanaka, M. Sugimoto, H. Takashima, M. Hada, and H. Nakatsuji, Bull. Chem. Soc. Jpn., 69, 953 (1996); C. C. Ballard, M. Hada, H. Kaneko, and H. Nakatsuji, Chem. Phys. Lett., 254, 170 (1996); H. Nakatsuji, M. Hada, H. Kaneko, and C. C. Ballard, Chem. Phys. Lett., 255, 195 (1996); M. Hada, H. Kaneko, and H. Nakatsuji, Chem. Phys. Lett., 261, 7 (1996). See also refs cited therein.
16. S. Tanaka, M. Sugimoto, H. Takashima, M. Hada, and H. Nakatsuji, Bull. Chem. Soc. Jpn., 69, 953 (1996); C. C. Ballard, M. Hada, H. Kaneko, and H. Nakatsuji, Chem. Phys. Lett., 254, 170 (1996); H. Nakatsuji, M. Hada, H. Kaneko, and C. C. Ballard, Chem. Phys. Lett., 255, 195 (1996); M. Hada, H. Kaneko, and H. Nakatsuji, Chem. Phys. Lett., 261, 7 (1996). See also refs cited therein.
17. S. Tanaka, M. Sugimoto, H. Takashima, M. Hada, and H. Nakatsuji, Bull. Chem. Soc. Jpn., 69, 953 (1996); C. C. Ballard, M. Hada, H. Kaneko, and H. Nakatsuji, Chem. Phys. Lett., 254, 170 (1996); H. Nakatsuji, M. Hada, H. Kaneko, and C. C. Ballard, Chem. Phys. Lett., 255, 195 (1996); M. Hada, H. Kaneko, and H. Nakatsuji, Chem. Phys. Lett., 261, 7 (1996). See also refs cited therein.
18. S. Tanaka, M. Sugimoto, H. Takashima, M. Hada, and H. Nakatsuji, Bull. Chem. Soc. Jpn., 69, 953 (1996); C. C. Ballard, M. Hada, H. Kaneko, and H. Nakatsuji, Chem. Phys. Lett., 254, 170 (1996); H. Nakatsuji, M. Hada, H. Kaneko, and C. C. Ballard, Chem. Phys. Lett., 255, 195 (1996); M. Hada, H. Kaneko, and H. Nakatsuji, Chem. Phys. Lett., 261, 7 (1996). See also refs cited therein.
19. Gaussian 94, Revision D. 4; Pople, J. A. Gaussian, Inc., Pittsburgh PA, 1995. Ab initio MO calculations were performed on Origin and/or Power Challenge L computers.
20. a) The energy minima could not be found near the structure of 7f and 7i, when the selenols were full optimized. Some appropriate torsional angles were fixed in the calculations to achieve the structure. b) The δc(Se) values of (6: 7) were (58.6: 11.1) for h and (109.5: 53.0) for i.
21. R. W. Taft (ed)," Progress in Physical Organic Chemistry," Wiley, New York (1976), Vol. 12.
22. The correlation becomes more complex, if the data of Y = CN is added, for example. It contains π(z)-and π(y)-orbitals which could interact with the p-type orbitals of the Se atom through the phenyl group.
23. Efforts were not made to obtain the best-fitted correlations. Details, containing the correlations in 6 and 7, will be reported elsewhere.