Skip to main content
SpringerLink
Log in

The Mills—Nixon and anomeric effects in 2,3-dihydro-1H-1,3,2-benzodiazaphospholes: a gas-phase electron diffraction study of C6H4(NMe)2PCl using quantum-chemical data and “a priori” force field

  • Published:
Russian Chemical Bulletin Aims and scope

Abstract

Geometric parameters and the force fields of the molecule of 2-chloro-1,3-dimethyl-2,3-dihydro-1H-1,3,2-benzodiazaphosphole, C6H4(NMe)2PCl (1), and the 1,3-dimethyl-2,3-dihydro-1H-1,3,2-benzodiazaphospholium cation, C6H4(NMe)2P+ (2), containing a dicoordinated P atom were calculated by the restricted Hartree—Fock (RHF) method using the 6-31G* and 6-311G** basis sets. Vibrational characteristics of the internuclear distances in molecule 1 were calculated using the “a priori” scaled force field. Structural analysis of the gas-phase electron diffraction data for this molecule was performed with inclusion of nonlinear kinematic effects at the first-order level of perturbation theory. Substantial lengthening of the P—Cl bond and conformational peculiarities of the phosphole fragment of molecule 1 are consistent with the expected manifestations of the anomeric effect. The type of partial localization of the π-bonds in the benzene fragment (relative weights of two resonance Kekule structures, or the Mills—Nixon effect) changes on going from covalent to ionized state of the P atom in the annelated five-membered ring.

This is a preview of subscription content, log in via an institution to check access.

Access this article

Log in via an institution

Price excludes VAT (USA)
Tax calculation will be finalised during checkout.

Instant access to the full article PDF.

Institutional subscriptions

Similar content being viewed by others

References

  1. L. S. Khaikin, O. E. Grikina, S. S. Kramarenko, E. A. Zhilinskaya, and B. I. Zhilinskii, Izv. Akad. Nauk, Ser. Khim., 2001, 1475 [Russ. Chem. Bull., Int. Ed., 2001, 50, 1550].

  2. L. S. Khaikin, V. A. Sipachev, A. V. Beklemishev, N. M. Pozdeev, E. A. Zhilinskaya, M. V. Proskurnina, and L. V. Vilkov, Vestn. Mosk. Univ., Ser. 2: Khim., 1997, 38, 222 [Moscow Univ. Bull., Ser. 2, Chem., 1997 (Engl. Transl.)].

    Google Scholar 

  3. L. S. Khaikin, O. E. Grikina, and L. V. Vilkov, J. Mol. Struct., 1982, 82, 115.

    Google Scholar 

  4. R. U. Lemieux, in Molecular Rearrangements, Ed. P. de Mayo, Interscience, New York, 1964, 2, 709.

    Google Scholar 

  5. C. Romers, C. Altona, H. R. Buys, and E. Havinga, Top. Stereochem., 1969, 4, 39.

    Google Scholar 

  6. N. S. Zefirov and N. M. Shekhtman, Usp. Khim., 1971, 40, 593 [Russ. Chem. Rev., 1971, 40, 315 (Engl. Transl.)].

    Google Scholar 

  7. N. S. Zefirov, Tetrahedron, 1977, 33, 3193.

    Google Scholar 

  8. S. Wolfe, A. Rauk, L. M. Tel, and I. G. Csizmadia, J. Chem. Soc., B, 1971, 136.

  9. A. J. Kirby, The Anomeric Effect and Related Stereoelectronic Effects at Oxygen, in Reactivity and Structure, 15, Springer, Berlin, 1983.

    Google Scholar 

  10. E. Cortez, R. Verastegui, J. Villarreal, and J. Laane, J. Am. Chem. Soc., 1993, 115, 12132.

    Google Scholar 

  11. D. Gudat, Eur. J. Inorg. Chem., 1998, 1087.

  12. O. S. Anisimova, A. I. Bokanov, E. N. Karpova, and V. I. Stepanov, Zh. Obshch. Khim., 1976, 46, 808 [J. Gen. Chem. USSR, 1976, 46 (Engl. Transl.)]

    Google Scholar 

  13. A. I. Bokanov and T. G. Edel´man, in Itogi nauki i tekhniki. Tekhnologiya organicheskikh veshchestv, 3, Khimiya i tekhnologiya organicheskikh krasitelei i promezhutochnykh produktov [Advances in Science and Technology. Chemistry and Technology of Organic Compounds. Vol. 3, Chemistry and Technology of Organic Dyes and Semi-Products], Ed. B. I. Stepanov, VINITI, Moscow, 1973, p. 27 (in Russian).

    Google Scholar 

  14. W. H. Mills and I. G. Nixon, J. Chem. Soc., 1930, 2510.

  15. F. H. Allen, Acta Crystallogr., 1981, B37, 900.

    Google Scholar 

  16. A. Domenicano, in Accurate Molecular Structures. Their Determination and Importance, Eds. A. Domenicano and I. Hargittai, Oxford University Press, Oxford, 1992.

    Google Scholar 

  17. N. Burford, A. I. Dipchand, B. W. Royan, and P. S. White, Acta Crystallogr., 1989, C45, 1485.

    Google Scholar 

  18. J. M. Barendt, E. G. Bent, R. C. Haltiwanger, and A. D. Norman, Inorg. Chem., 1989, 28, 2334.

    Google Scholar 

  19. S. M. Young, A. Tarassoli, J. M. Barendt, C. A. Squiers, F. Barthelemy, R. Schaeffer, R. C. Haltiwanger, and A. D. Norman, Inorg. Chem., 1994, 33, 2748.

    Google Scholar 

  20. E. G. Bent, R. C. Haltiwanger, and A. D. Norman, Inorg. Chem., 1990, 29, 4310.

    Google Scholar 

  21. J. M. Barendt, E. G. Bent, R. C. Haltiwanger, C. A. Squiers, and A. D. Norman, Inorg. Chem., 1989, 28, 4425.

    Google Scholar 

  22. L. S. Khaikin, A. V. Abramenkov, V. V. Smirnov, and L. V. Vilkov, 11th Austin Symp. on Molecular Structure (Austin, Texas, USA, March 3-5, 1986), Austin, 1986, S15, 99.

  23. G. Fogarasi and P. Pulay, Ab initio Calculation of Force Field and Vibrational Spectra, in Vibrational Spectra and Structure, Ed. J. R. Durig, Elsevier, Amsterdam, 1985, 14, 125.

    Google Scholar 

  24. Yu. N. Panchenko, Izv. Akad. Nauk, Ser. Khim., 1996, 800 [Russ. Chem. Bull., 1996, 45, 753 (Engl. Transl.)].

  25. P. Pulay, G. Fogarasi, F. Pang, and J. E. Boggs, J. Am. Chem. Soc., 1979, 101, 2550.

    Google Scholar 

  26. V. I. Pupyshev, Yu. N. Panchenko, Ch. W. Bock, and G. Pongor, J. Chem. Phys., 1991, 94, 1247.

    Google Scholar 

  27. Yu. N. Panchenko, G. R. De Mare, and V. I. Pupyshev, J. Phys. Chem., 1995, 99, 17544.

    Google Scholar 

  28. N. F. Stepanov, G. R. De Mare, and Yu. N. Panchenko, J. Mol. Struct. (THEOCHEM), 1995, 342, 9.

    Google Scholar 

  29. V. I. Pupyshev, N. F. Stepanov, S. V. Krasnoshchiokov, G. R. De Mare, and Yu. N. Panchenko, J. Mol. Struct., 1996, 376, 363.

    Google Scholar 

  30. H. Sellers, P. Pulay, and J. E. Boggs, J. Am. Chem. Soc., 1985, 107, 6487.

    Google Scholar 

  31. L. S. Khaikin, O. E. Grikina, V. A. Shlyapochnikov, and J. E. Boggs, Izv. Akad. Nauk, Ser. Khim., 1994, 2106 [Russ. Chem. Bull., 1994, 43, 1987 (Engl. Transl.)].

  32. L. S. Khaikin, O. E. Grikina, V. A. Shlyapochnikov, L. V. Vilkov, and Ch. W. Bock, Izv. Akad. Nauk, Ser. Khim., 1995, 2135 [Russ. Chem. Bull., 1995, 44, 2039 (Engl. Transl.)].

  33. L. S. Khaikin, O. E. Grikina, V. I. Perevozchikov, S. S. Kramarenko, V. A. Shlyapochnikov, and J. E. Boggs, Izv. Akad. Nauk, Ser. Khim., 1998, 1557 [Russ. Chem. Bull., 1998, 47, 1514 (Engl. Transl.)].

  34. V. A. Sipachev, L. S. Khaikin, O. E. Grikina, V. S. Nikitin, and M. Traetteberg, J. Mol. Struct., 2000, 523, 1.

    Google Scholar 

  35. M. Traetteberg, L. S. Khaikin, O. E. Grikina, J. F. Liebman, and M. Hulce, J. Mol. Struct., 2001, 559, 295.

    Google Scholar 

  36. L. S. Khaikin, O. E. Grikina, V. A. Sipachev, and M. Traetteberg, J. Mol. Struct., 2001, 567-568, 85.

    Google Scholar 

  37. A. Kh. Plyamovatyi, S. A. Katsuba, M. V. Proskurnina, L. S. Khaikin, O. E. Grikina, M. Alcolea Palafox, R. R. Shagidullin, and J. E. Boggs, XVI Austin Symp. on Molecular Structure (Austin, Texas USA, March 2-4, 1996), Austin, 1996, SN24, 145.

  38. V. A. Shlyapochnikov, L. S. Khaikin, O. E. Grikina, C. W. Bock, and L. V. Vilkov, J. Mol. Struct., 1994, 326, 1; (b) W. B. Collier, I. Magdo, and T. D. Klots, J. Chem. Phys., 1999, 110, 5710.

    Google Scholar 

  39. W. B. Jennings, D. Randall, S. D. Worley, and J. H. Hargis, J. Chem. Soc., Perkin Trans. 2, 1981, 1411.

  40. L. V. Vilkov, A. V. Golubinskii, V. S. Mastryukov, N. I. Sadova, L. S. Khaikin, and I. Hargittai, in Sovremennye problemy fizicheskoi khimii [Modern Problems of Physical Chemistry], Vol. 11, Eds. Ya. I. Gerasimov and P. A. Akishin, Izd-vo MGU, Moscow, 1979, p. 59 (in Russian).

    Google Scholar 

  41. H. E. Swanson and R. K. Fuyat, NBS Circular 539, 1953, 2, p. 25; Card No. 5-0664.

    Google Scholar 

  42. A. W. Ross, M. Fink, and R. H. Hilderbrandt, International Tables for Crystallography, Int. Union of Crystallography, Kluwer, Boston (MA), 1992, 4, 245.

    Google Scholar 

  43. K. Kuchitsu, M. Nakata, and S. Yamamoto, in Stereochemical Applications of Gas Phase Electron Diffraction, Part A, Electron Diffraction Technique, Eds. I. Hargittai and M. Hargittai,VCH, New York, 1988, Ch. 7, 227.

    Google Scholar 

  44. K. Hedberg and M. Iwasaki, J. Chem. Phys., 1962, 36, 589.

    Google Scholar 

  45. V. A. Sipachev, Adv. Mol. Struct. Res., 5, Eds. I. Hargittai and M. Hargittai, JAI, Greenwich, 1999, 323.

    Google Scholar 

  46. V. A. Sipachev, J. Mol. Struct., 1985, 121, Suppl.: Theochem., 1985, 22, 143.

  47. V. A. Sipachev, J. Mol. Struct., 2001, 567-568, 67.

    Google Scholar 

  48. L. S. Bartell, J. Chem. Phys., 1963, 38, 1827.

    Google Scholar 

  49. M. Iwasaki and K. Hedberg, J. Chem. Phys., 1962, 36, 2961.

    Google Scholar 

  50. V. A. Sipachev, Struct. Chem., 2000, 11, 167.

    Google Scholar 

  51. G. Gundersen, S. Samdal, and H. M. Seip, Least Squares Structural Refinement Program Based on Gas Electron Diffraction Data, Parts I-III, Dept. of Chemistry, University of Oslo, Norway, 1980-1981, 77 pp.

    Google Scholar 

  52. M. J. Frisch, G. W. Trucks, M. Head-Gordon, P. M. W. Gill, M. W. Wong, J. B. Foresman, B. J. Johnson, H. B. Schlegel, M. A. Robb, E. S. Peplogle, R. Gomperts, J. L. Anders, K. Raghavachari, J. S. Binkley, C. Gonzales, R. L. Martin, D. J. Fox, D. J. Defrees, J. Baker, J. J. P. Stewart, and J. A. Pople, GAUSSIAN-92, Revision C, Gaussian Inc., Pittsburgh (PA), 1992.

    Google Scholar 

  53. S. V. Krasnoshchekov, A. V. Abramenkov, and Yu. N. Panchenko, Zh. Fiz. Khim., 1997, 71, 497 [Russ. J. Phys. Chem., 1997, 71 (Engl. Transl.)].

    Google Scholar 

  54. S. V. Krasnoshchekov, A. V. Abramenkov, and Yu. N. Panchenko, Vestn. Mosk. Univ., Ser. 2: Khim., 1985, 26, 29 [Moscow Univ. Bull., Ser. 2, Chem., 1985 (Engl. Transl.)].

    Google Scholar 

  55. M. Veljkovic, O. Neskovic, M. Miletic, D. Golobocanin, and K. F. Zmbov, Vestn. Slov. Kem. Drus., 1986, 33 (Suppl.), 271.

    Google Scholar 

  56. K. Kuchitsu and S. J. Cyvin, in Molecular Structures and Vibrations, Ed. S. J. Cyvin, Elsevier, Amsterdam, 1972, Ch. 12, 183.

    Google Scholar 

  57. L. S. Khaikin and L. V. Vilkov, Usp. Khim., 1971, 41, 2224 [Russ. Chem. Rev., 1971, 41 (Engl. Transl.).

    Google Scholar 

Download references

Author information

Authors and Affiliations

  1. Department of Chemistry, M. V. Lomonosov Moscow State University, Leninskie Gory, 119899, Moscow, Russian Federation

    L. S. Khaikin, O. E. Grikina & L. V. Vilkov

  2. Littoral University, F-59140, Dunkirk, France

    E. A. Zhilinskaya

  3. Littoral University, F-59140, Dunkirk, France

    B. I. Zhilinskii

Authors
  1. L. S. Khaikin
    View author publications

    You can also search for this author in PubMed Google Scholar

  2. O. E. Grikina
    View author publications

    You can also search for this author in PubMed Google Scholar

  3. E. A. Zhilinskaya
    View author publications

    You can also search for this author in PubMed Google Scholar

  4. B. I. Zhilinskii
    View author publications

    You can also search for this author in PubMed Google Scholar

  5. L. V. Vilkov
    View author publications

    You can also search for this author in PubMed Google Scholar

Rights and permissions

Reprints and permissions

About this article

Cite this article

Khaikin, L.S., Grikina, O.E., Zhilinskaya, E.A. et al. The Mills—Nixon and anomeric effects in 2,3-dihydro-1H-1,3,2-benzodiazaphospholes: a gas-phase electron diffraction study of C6H4(NMe)2PCl using quantum-chemical data and “a priori” force field. Russian Chemical Bulletin 51, 2014–2025 (2002). https://doi.org/10.1023/A:1021699523986

Download citation

  • Issue Date:

  • DOI: https://doi.org/10.1023/A:1021699523986

Search

Navigation