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Effect of counterions on hypervalent interactions in prereaction complexes of S N 2 reactions of bisphenoid compounds of the second and third period elements

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Abstract

The electronic and molecular structures of the (LiF) n XF m complexes (X = C, N, O, F, Si, P, S, Cl; m = 1–4, n = 0, 1, 3) were studied by the ab initio (MP2(full)/6-311+G*) and density functional theory (B3LYP/6-311+G*) methods. All bisphenoid anionic structures XF m − (X = C, N, O, F, Si, P, S, Cl; m = 2–5) of elements of the second and third periods, except carbon fluorides, are most stable in the hypervalent state of atoms with strongly elongated axial bonds. Carbon tetrafluoride forms a stable intermolecular F−...CF4 complex. In all cases of addition of the Li atom as a counterion, the most stable intermolecular complex of lithium fluoride with fluorides of elements is stabilized by the hypervalent interaction. In all cases when the counterion is complicated to lithium trifluoride, except for (LiF)3CF4 and (LiF)3NF3, the hypervalent structure with equal and elongated X-F axial bonds is stabilized. In the cases of the (LiF)3CF4 and (LiF)3NF3 complexes, the prereaction structures bound by the strong hypervalent interaction are stabilized.

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References

  1. J. I. Musher, Angew. Chem., Int. Ed., 1969, 8, 54.

    Article  CAS  Google Scholar 

  2. A. Haaland, Angew. Chem., Int. Ed., 1989, 28, 992.

    Article  Google Scholar 

  3. V. I. Minkin, R. M. Minyaev, Chem. Rev., 2001, 101, 1247.

    Article  CAS  Google Scholar 

  4. R. M. Minyaev, V. I. Minkin, Canad. J. Chem., 1998, 76, 81.

    Article  Google Scholar 

  5. V. I. Minkin, Ross. Khim. Zh., 1999, 43, 10 [Mendeleev Chem. J. (Engl. Transl.), 1999, 43].

    CAS  Google Scholar 

  6. A. E. Reed, P. v. R. Schleyer, J. Am. Chem. Soc., 1990, 112, 1434.

    Article  CAS  Google Scholar 

  7. G. C. Pimentel, J. Chem. Phys., 1951, 19, 446.

    Article  CAS  Google Scholar 

  8. R. J. Hach, R. E. Rundle, J. Am. Chem. Soc., 1951, 73, 4321.

    Article  CAS  Google Scholar 

  9. R. E. Rundle, J. Am. Chem. Soc., 1963, 85, 112.

    Article  CAS  Google Scholar 

  10. A. E. Reed, L. A. Curtiss, F. Weinhold, Chem. Rev., 1988, 88, 899.

    Article  CAS  Google Scholar 

  11. G. M. Landrum, N. Goldberg, R. Hoffmann, R. M. Minyaev, New J. Chem., 1998, 22, 883.

    Article  CAS  Google Scholar 

  12. G. M. Landrum, N. Goldberg, R. Hoffmann, J. Chem. Soc., Dalton Trans., 1997, 3605.

    Google Scholar 

  13. R. M. Minyaev, V. I. Minkin, Russ. Chem. Bull. (Engl. Transl.), 1999, 48, 1234 [Izv. Akad. Nauk, Ser. Khim., 1999, 1246].

    Article  CAS  Google Scholar 

  14. A. A. Milov, R. M. Minyaev, V. I. Minkin, Zh. Org. Khim., 2003, 39, 372 [Russ. J. Org. Chem. (Engl. Transl.), 2003, 39, 340].

    Google Scholar 

  15. M. G. Voronkov, O. M. Trofimova, Yu. I. Bolgova, N. F. Chernov, Russ. Chem. Rev., 2007, 76, 825.

    Article  CAS  Google Scholar 

  16. V. V. Negrebetskii, S. N. Tandura, Yu. I. Baukov, Russ. Chem. Rev., 2009, 78, 21 [Usp. Khim., 2009, 78, 24].

    Article  Google Scholar 

  17. J. N. Verkade, Acc. Chem. Res., 1993, 26, 483.

    Article  CAS  Google Scholar 

  18. R. R. Holmes, Chem. Rev., 1996, 96, 927.

    Article  CAS  Google Scholar 

  19. V. I. Minkin, R. M. Minyaev, A. A. Milov, T. N. Gribanova, Russ. Chem. Bull. (Int. Ed.), 2001, 50, 2028 [Izv. Akad. Nauk, Ser. Khim., 2001, 1938].

  20. R. M. Minyaev, V. I. Minkin, Mendeleev Commun., 2000, 10, 173.

    Article  Google Scholar 

  21. O. N. Ventura, E. L. Coitino, A. Lledos, J. Bertran, J. Comput. Chem., 1992, 13, 1037 (and references cited therein).

    Article  CAS  Google Scholar 

  22. J. L. Wilbur, J. I. Brauman, J. Am. Chem. Soc., 1994, 116, 5839.

    Article  CAS  Google Scholar 

  23. K.-y. Akiba, M. Yamashita, Y. Yamamoto, S. Nagase, J. Am. Chem. Soc., 1999, 121, 10644.

    Article  CAS  Google Scholar 

  24. M. Bühl, H. F. Schaefer, III, J. Am. Chem. Soc., 1993, 115, 364; M. Bühl, H. F. Schaefer, III, J. Am. Chem. Soc., 1993, 115, 9143.

    Article  Google Scholar 

  25. M. N. Glukhovtsev, A. Pross, L. Radom, J. Am. Chem. Soc., 1995, 117, 9012.

    Article  CAS  Google Scholar 

  26. Y. Ren, H. Basch, S. Hoz, J. Org. Chem., 2002, 67, 5891.

    Article  Google Scholar 

  27. J. Yang, Y. Ren, H.-j. Zhu, S.-Y. Chu, Int. J. Mass Spectrom., 2003, 229, 199.

    Article  CAS  Google Scholar 

  28. R. Gareyev, S. Kato, V. M. Bierbaum, J. Am. Soc. Mass. Spectrom., 2001, 12, 139.

    Article  CAS  Google Scholar 

  29. R. Ulbrich, M. Famulok, F. Bosold, G. Boche, Tetrahedron Lett., 1990, 31, 1689.

    Article  CAS  Google Scholar 

  30. J. S. Helmick, K. A. Martin, J. L. Heinrich, M. Novak, J. Am. Chem. Soc., 1991, 113, 3459.

    Article  CAS  Google Scholar 

  31. M. Novak, K. A. Martin, J. L. Heinrich, J. Org. Chem., 1989, 54, 5430.

    Article  CAS  Google Scholar 

  32. M. Famulok, F. Bosold, G. Boche, Angew. Chem., Int. Ed., 1989, 28, 337.

    Article  Google Scholar 

  33. P. Beak, J. Li, J. Am. Chem. Soc., 1991, 113, 2796.

    Article  CAS  Google Scholar 

  34. Y. Ren, J. L. Wolk, S. Hoz, Int. J. Mass Spectrom., 2002, 220, 1.

    Article  CAS  Google Scholar 

  35. T. I. Sðlling, A. Pross, L. Radom, Int. J. Mass Spectrom., 2001, 210–211, 1.

    Google Scholar 

  36. D. C. Mullhearn, S. M. Bachrach, J. Am. Chem. Soc., 1996, 118, 9415.

    Article  Google Scholar 

  37. S. M. Bachrach, B. D. Gailbreath, J. Org. Chem., 2001, 66, 2005.

    Article  CAS  Google Scholar 

  38. S. M. Bachrach, A. C. Chamberlin, J. Org. Chem., 2003, 68, 4743.

    Article  CAS  Google Scholar 

  39. L. D. Quin, A Guide to Organophosphorus Chemistry, John Wiley and Sons, New York, 2000, 408 pp.

    Google Scholar 

  40. R. R. Holmes, A. Chandrasekaran, N. V. Timosheva, Phosphorus, Sulfur, Silicon Relat. Elem., 2008, 183, 209.

    Article  CAS  Google Scholar 

  41. P. A. Cahill, C. E. Dykstra, J. C. Martin, J. Am. Chem. Soc., 1985, 107, 6359.

    Article  CAS  Google Scholar 

  42. C. S. Ewig, J. R. Van Wazer, J. Am. Chem. Soc., 1990, 112, 109.

    Article  CAS  Google Scholar 

  43. G. L. Heard, C. J. Marsden, G. E. Scuseria, J. Phys. Chem., 1992, 96, 4359.

    Article  CAS  Google Scholar 

  44. T. Kar, E. Sánchez Marcos, Chem. Phys. Lett., 1992, 192, 14.

    Article  CAS  Google Scholar 

  45. T. G. Wright, E. P. F. Lee, Mol. Phys., 1993, 79, 995.

    Article  CAS  Google Scholar 

  46. N. O. J. Malcolm, J. J. W. McDouall, J. Phys. Chem., 1996, 100, 10131.

    Article  CAS  Google Scholar 

  47. F. Mota, J. J. Novoa, J. Chem. Phys., 1996, 105, 8777.

    Article  CAS  Google Scholar 

  48. J. Czernek, O. Zivny, J. Chem. Phys., 2008, 129, 194305.

    Article  Google Scholar 

  49. S. Riedel, T. Köchner, X. Wang, L. Andrews, Inorg. Chem., 2010, 49, 7156.

    Article  CAS  Google Scholar 

  50. A. Artau, K. E. Nizzi, B. T. Hill, L. S. Sunderlin, P. G. Wenthold, J. Am. Chem. Soc., 2000, 122, 10667.

    Article  CAS  Google Scholar 

  51. S. Harder, A. Streitwieser, J. T. Petty, P. v. R. Schleyer, J. Am. Chem. Soc., 1995, 117, 3253.

    Article  CAS  Google Scholar 

  52. Y. Ren, S.-Y. Chu, J. Phys. Chem. A, 2004, 108, 7079.

    Article  CAS  Google Scholar 

  53. Y. Ren, S.-Y. Chu, Chem. Phys. Lett., 2003, 376, 524.

    Article  CAS  Google Scholar 

  54. B. S. Ault, L. Andrews, J. Am. Chem. Soc., 1976, 98, 1591.

    Article  CAS  Google Scholar 

  55. B. S. Ault, L. Andrews, Inorg. Chem., 1977, 16, 2024.

    Article  CAS  Google Scholar 

  56. A. A. Tuinman, A. A. Gakh, R. J. Hinde, R. N. Compton, J. Am. Chem. Soc., 1999, 121, 8397.

    Article  CAS  Google Scholar 

  57. A. Artau, K. E. Nizzi, B. T. Hill, L. S. Sunderlin, P. G. Wenthold, J. Am. Chem. Soc., 2000, 122, 10667.

    Article  CAS  Google Scholar 

  58. D. J. Tozer, C. P. Sosa, Mol. Phys., 1997, 90, 515.

    Article  Google Scholar 

  59. J. Frisch, G. W. Trucks, H. B. Schlegel, G. E. Scuseria, M. A. Robb, J. R. Cheeseman, J. A. Montgomery, Jr., T. Vreven, K. N. Kudin, J. C. Burant, J. M. Millam, S. S. Iyengar, J. Tomasi, V. Barone, B. Mennucci, M. Cossi, G. Scalmani, N. Rega, G. A. Petersson, H. Nakatsuji, M. Hada, M. Ehara, K. Toyota, R. Fukuda, J. Hasegawa, M. Ishida, T. Nakajima, Y. Honda, O. Kitao, H. Nakai, M. Klene, X. Li, J. E. Knox, H. P. Hratchian, J. B. Cross, C. Adamo, J. Jaramillo, R. Gomperts, R. E. Stratmann, O. Yazyev, A. J. Austin, R. Cammi, C. Pomelli, J. W. Ochterski, P. Y. Ayala, K. Morokuma, G. A. Voth, P. Salvador, J. J. Dannenberg, V. G. Zakrzewski, S. Dapprich, A. D. Daniels, M. C. Strain, O. Farkas, D. K. Malick, A. D. Rabuck, K. Raghavachari, J. B. Foresman, J. V. Ortiz, Q. Cui, A. G. Baboul, S. Clifford, J. Cioslowski, B. B. Stefanov, G. Liu, A. Liashenko, P. Piskorz, I. Komaromi, R. L. Martin, D. J. Fox, T. Keith, M. A. Al-Laham, C. Y. Peng, A. Nanayakkara, M. Challacombe, P. M. W. Gill, B. Johnson, W. Chen, M. W. Wong, C. Gonzalez, J. A. Pople, Gaussian-03, Revision C.02, Gaussian, Inc., Pittsburgh (PA), 2004.

    Google Scholar 

  60. J. B. Foresman, A. Frisch, Exploring Chemistry with Electronic Structure Methods, 2nd ed., Gaussian, Inc., Pittsburg, 1996, 302 pp.

    Google Scholar 

  61. R. M. Minyaev, Russ. Chem. Rev., 1994, 63, 883.

    Article  Google Scholar 

  62. G. A. Zhurko, ChemCraft, Tool for Treatment of the Chemical Data; www.chemcraftprog.com.

  63. J. A. Deiters, R. R. Holmes, J. Am. Chem. Soc., 1990, 112, 7197.

    Article  CAS  Google Scholar 

  64. D. Schrobilgen, R. Krebs, Inorg. Chem., 1984, 23, 1378.

    Article  Google Scholar 

  65. K. O. Christe, D. A. Dixon, P. A. Mercier, J. C. P. Sanders, G. J. Schrobilgen, W. W. Wilson, J. Am. Chem. Soc., 1994, 116, 2850.

    Article  CAS  Google Scholar 

  66. G. L. Gutsev, T. Ziegler, Inorg. Chem., 1992, 31, 1909.

    Article  CAS  Google Scholar 

  67. I. Anusiewicz, S. Freza, C. Sikorska, P. Skurski, Chem. Phys. Lett., 2010, 493, 234.

    Article  CAS  Google Scholar 

  68. C.-K. Law, S.-H. Chien, W.-K. Li, J. Phys. Chem. A, 2002, 106, 11271.

    Article  CAS  Google Scholar 

  69. M. Hargittai, I. Hargittai, The Molecular Geometries of Coordination Compounds in Vapour Phase, Akademia Kiado, Budapest, 1975.

    Google Scholar 

  70. K. S. Krasnov, N. V. Filippenko, V. A. Bobkova, Molekulyarnye postoyannye neorganicheskikh soedinenii [Molecular Constants of Inorganic Compounds], Khimiya, Leningrad, 1979, 446 pp. (in Russian).

    Google Scholar 

  71. M. W. Chase, Jr., NIST-JANAF Termocheical Tables, 4th ed., J. Phys. Chem. Ref. Data, Monograph 9, 1998.

    Google Scholar 

  72. L. Jörissen, H. Prinz, W. A. Kreiner, Ch. Wenger, G. Pierre, G. Magerl, W. Schupita, Can. J. Phys., 1989, 67, 532.

    Article  Google Scholar 

  73. S. Creve, M. T. Nguyen, Chem. Phys. Lett., 1997, 273, 199.

    Article  CAS  Google Scholar 

  74. A. E. S. Miller, T. M. Miller, A. A. Viggiano, R. A. Morris, J. M. Van Doren, S. T. Arnold, J. Paulson, J. Chem. Phys., 1995, 102, 8865.

    Article  CAS  Google Scholar 

  75. L. N. Sidorov, Russ. Chem. Rev., 1982, 51, 356.

    Article  Google Scholar 

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  1. Research Institute of Physical and Organic Chemistry, Southern Federal University, 194/2 prosp. Stachki, 344090, Rostov-on-Don, Russian Federation

    I. V. Getmanskii, R. M. Minyaev & V. I. Minkin

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  1. I. V. Getmanskii
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  2. R. M. Minyaev
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  3. V. I. Minkin
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Correspondence to R. M. Minyaev.

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Published in Russian in Izvestiya Akademii Nauk. Seriya Khimicheskaya, No. 11, pp. 2019–2031, November, 2012.

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Getmanskii, I.V., Minyaev, R.M. & Minkin, V.I. Effect of counterions on hypervalent interactions in prereaction complexes of S N 2 reactions of bisphenoid compounds of the second and third period elements. Russ Chem Bull 61, 2036–2048 (2012). https://doi.org/10.1007/s11172-012-0285-1

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