Pyramidal inversion energies and conformational analysis of chalcogen-onium imides based on ab initio MO calculations †

Abstract

Ab initio MO calculations of sulfonium, selenonium and telluronium imides R¹₂X→NR² (X = S, Se, Te) have been performed to obtain their pyramidal inversion (vertex inversion) barriers and rotation barriers around the chalcogen–nitrogen bonds. The activation energies for the pyramidal inversion reaction, which is an important pathway for racemization of the chiral chalcogen-onium imides when the two R¹ groups are different, depend on the substituents, R¹ and R², on the chalcogen and nitrogen atoms. The computations indicated that the telluronium imides require larger activation energies for the pyramidal inversion reaction than those of corresponding sulfonium and selenonium imides. The rotation barriers around the chalcogen–nitrogen bonds, which is the conformational exchange pathway between two local minima of the chalcogen-onium imides, showed the opposite trend.

References

1. For reviews: T. Shimizu and N. Kamigata, Rev. Heteroat. Chem., 1998, 18, 11; T. Shimizu and N. Kamigata, Org. Prep. Proced. Int., 1997, 29, 603.
2. For a review: N. Kamigata and T. Shimizu, Rev. Heteroat. Chem., 1991, 4, 226.
3. T. Shimizu and M. Kobayashi, Chem. Lett., 1986, 161; T. Shimizu and M. Kobayashi, Bull. Chem. Soc. Jpn., 1986, 59, 2654; T. Shimizu and M. Kobayashi, J. Org. Chem., 1987, 52, 3399; T. Shimizu, M. Kobayashi and N. Kamigata, Bull. Chem. Soc. Jpn., 1988, 61, 3761; T. Shimizu, M. Kobayashi and N. Kamigata, Sulfur Lett., 1988, 8, 61; T. Shimizu, M. Kobayashi and N. Kamigata, Bull. Chem. Soc. Jpn., 1989, 62, 2099; T. Shimizu, K. Kikuchi, Y. Ishikawa, I. Ikemoto, M. Kobayashi and N. Kamigata, J. Chem. Soc., Perkin Trans. 1, 1989, 597.
4. N. Kamigata, Y. Nakamura, H. Matsuyama and T. Shimizu, Chem. Lett., 1991, 249; N. Kamigata, Y. Nakamura, K. Kikuchi, I. Ikemoto, T. Shimizu and H. Matsuyama, J. Chem. Soc., Perkin Trans. 1, 1992, 1721.
5. M. Kobayashi, K. Koyabu, T. Shimizu, K. Umemura and H. Matsuyama, Chem. Lett., 1986, 2117.
6. T. Shimizu, T. Urakubo, P. Jin, M. Kondo, S. Kitagawa and N. Kamigata, J. Organomet. Chem., 1997, 539, 171.
7. T. Shimizu, Y. Yamazaki, H. Taka and N. Kamigata, J. Am. Chem. Soc., 1997, 119, 5966.
8. N. Kamigata, A. Matsuhisa, H. Taka and T. Shimizu, J. Chem. Soc., Perkin Trans. 1, 1995, 821.
9. T. Shimizu, T. Urakubo and N. Kamigata, Chem. Lett., 1996, 297; T. Shimizu, T. Urakubo and N. Kamigata, J. Org. Chem., 1996, 61, 8032.
10. K. K. Andersen, J. W. Folly, T. I. Perkins, W. Gaffield and N. E. Papanikolau, J. Am. Chem. Soc., 1964, 86, 5637; K. Mislow, M. M. Green, P. Laur, J. T. Melillo, T. Simmons and A. L. Ternary, Jr., J. Am. Chem. Soc., 1965, 87, 1958; S. Zhao, O. Samuel and H. B. Kagan, Tetrahedron, 1987, 43, 5135.
11. D. Darwish and R. L. Tomilson, J. Am. Chem. Soc., 1968, 90, 5938; S. J. Campbell and D. Darwish, Can. J. Chem., 1974, 52, 2953; M. Moriyama, S. Oae, T. Numata and N. Furukawa, Chem. Ind., 1976, 163.
12. K. K. Andersen, R. L. Caret and D. L. Ladd, J. Org. Chem., 1976, 41, 3096; K. K. Andersen, The Chemistry of the Sulfonium Group, eds. C. J. M. Stirling and S. Patai, Wiley, New York, 1981, pp. 229–266.
13. J. Day and D. J. Cram, J. Am. Chem. Soc., 1965, 87, 4398; M. Moriyama, T. Yoshimura, N. Furukawa, T. Numata and S. Oae, Tetrahedron, 1976, 32, 3003.
14. N. Kamigata, H. Taka, A. Matsuhisa, H. Matsuyama and T. Shimizu, J. Chem. Soc., Perkin Trans. 1, 1994, 2257; N. Kamigata, H. Taka, A. Matsuhisa and T. Shimizu, J. Phys. Org. Chem., 1995, 8, 139.
15. T. Shimizu, N. Seki, H. Taka and N. Kamigata, J. Org. Chem., 1996, 61, 6013.
16. T. Shimizu, A. Matsuhisa, N. Kamigata and S. Ikuta, J. Chem. Soc., Perkin Trans. 1, 1995, 1805.
17. C. Møller and M. S. Plesset, Phys. Rev., 1934, 46, 618.
18. A. Schaefer, H. Horn and R. Ahlrichs, J. Chem. Phys., 1992, 97, 2571; A. Schaefer, G. Huber and R. Ahlrichs, J. Chem. Phys., 1994, 100, 5829.
19. A. Leininger, A. Nicklas, H. Stoll, M. Dolg and P. Schwerdtfeger, J. Chem. Phys., 1996, 105, 1052 and references cited therein.
20. D. E. Woon and T. H. Dunning, Jr., J. Chem. Phys., 1993, 98, 1358.
21. J. Cizek, Adv. Chem. Phys., 1969, 14, 35; R. J. Bartlett and G. D. Purvis, Int. J. Quantum Chem., 1978, 14, 516; J. A. Pople, R. Krishnan, M. Head-Gordon, K. Raghavachari and G. W. Trucks, Chem. Phys. Lett., 1989, 164, 185.
22. M. J. Frisch, G. W. Trucks, H. B. Schlegel, G. E. Scuseria, M. A. Robb, J. R. Cheeseman, V. G. Zakrzewski, J. A. Montgomery, Jr., R. E. Stratmann, J. C. Burant, S. Dapprich, J. M. Millam, A. D. Daniels, K. N. Kudin, M. C. Strain, O. Farkas, J. Tomasi, V. Barone, M. Cossi, R. Cammi, B. Mennucci, C. Pomelli, C. Adamo, S. Clifford, J. Ochterski, G. A. Petersson, P. Y. Ayala, Q. Cui, K. Morokuma, D. K. Malick, A. D. Rabuck, K. Raghavachari, J. B. Foresman, J. Cioslowski, J. V. Ortiz, B. B. Stefanov, G. Liu, A. Liashenko, P. Piskorz, I. Komaromi, R. Gomperts, R. L. Martin, D. J. Fox, T. Keith, M. A. Al-Laham, C. Y. Peng, A. Nanayakkara, C. Gonzalez, M. Challacombe, P. M. W. Gill, B. Johnson, W. Chen, M. W. Wong, J. L. Andres, C. Gonzalez, M. Head-Gordon, E. S. Replogle and J. A. Pople, Gaussian, Inc., Pittsburgh, PA, 1998.
23. For other methods basis sets employed LANL2DZ: P. J. Hay and W. R. Wadt, J. Chem. Phys., 1985, 82, 270; W. R. Wadt and P. J. Hay, J. Chem. Phys., 1985, 82, 284; P. J. Hay and W. R. Wadt, J. Chem. Phys., 1985, 82, 299 6-31G: R. Ditchfield, W. J. Hehre and J. A. Pople, J. Chem. Phys., 1971, 54, 724; W. J. Hehre, R. Ditchfield and J. A. Pople, J. Chem. Phys., 1972, 56, 2257; P. C. Hariharan and J. A. Pople, Mol. Phys., 1974, 27, 209; M. S. Gordon, Chem. Phys. Lett., 1980, 76, 209; P. C. Hariharan and J. A. Pople, Theor. Chim. Acta, 1974, 28, 213 6-311G: A. D. McLean and G. S. Chandler, J. Chem. Phys., 1980, 72, 5639; R. Krishnan, J. S. Binkley, R. Seeger and J. A. Pople, J. Chem. Phys., 1980, 72, 650 ++: T. Clark, J. Chandrasekhar, G. W. Spitznagel and P. V. R. Schleyer, J. Comput. Chem., 1983, 4, 194 3df,2p: M. J. Frish, J. A. Pople and J. S. Binkley, J. Chem. Phys., 1984, 80, 3265 cc-pVTZ: T. H. Dunning, Jr., J. Chem. Phys., 1989, 90, 1007; R. A. Kendall, T. H. Dunning, Jr. and R. J. Harrison, J. Chem. Phys., 1992, 96, 6796; K. A. Peterson, D. E. Wood and T. H. Dunning, Jr., J. Chem. Phys., 1994, 100, 7410.
24. For examples: A. Kálmán, K. Sasvári and Á. Kucsman, J. Chem. Soc., Chem. Commun., 1971, 1447; A. Kálmán, K. Sasvári and Á. Kucsman, Acta Crystallogr., Sect. B, 1973, 29, 1241; A. F. Cameron, F. D. Duncanson and D. G. Morris, Acta Crystallogr., Sect. B, 1976, 32, 1998; A. Kálmán, T. Koritsánszky, I. Kapovits and Á. Kucsman, Acta Crystallogr., Sect. B, 1982, 38, 1843.
25. N. G. Furmanova, R. G. Gerr, V. P. Krasnov and V. I. Naddaka, Zh. Strukt. Khim., 1984, 25, 166; H. W. Roesky, K.-L. Weber, U. Seseke, W. Pinkert, M. Noltemeyer, W. Clegg and G. M. Sheldrick, J. Chem. Soc., Dalton Trans., 1985, 565.
26. N. G. Furmanova, V. I. Naddaka and V. P. Krasnov, Zh. Strukt. Khim., 1981, 22, 118.