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Quantum-chemical study of intramolecular spin-forbidden rearrangements of the transition metal chelate complexes

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Abstract

An overview of quantum-chemical methods of studying the spin-forbidden reactions is presented. It was shown that HF and MP2 methods overestimate stabilization of the high-spin states whereas DFT methods with the use of LSDA and CGA functionals underestimate these states. Hybrid exchange-correlation density functionals B3P86 and B3LYP give the best agreement with the experimental data. The intramolecular spin-forbidden rearrangement of bis-chelate Ni(II) and Co(II) complexes was studied using the B3LYP/6-311++G (d,p) method.

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References

  1. Gaspar, A.B., Ksenofontov, V., Seredyuk, M., and Gutlich, P., Coord. Chem. Rev., 2005, vol. 249, pp. 2661–2676.

    Article  CAS  Google Scholar 

  2. Computational Organometallic Chemistry, Cundari, T.R., Ed., CRC, 2001.

  3. Gerstman, B.S. and Sungar, N., J. Chem. Phys., 1992, vol. 96, pp. 387–398.

    Article  CAS  Google Scholar 

  4. Shreve, A.P., Franzen, S., Simpson, M.C., and Dyer, R.B., J. Phys. Chem., B, 1999, vol. 103, pp. 7969–7975.

    Article  CAS  Google Scholar 

  5. Liu, C., Zhang, D., and Bian, W., J. Phys. Chem., A, 2003, vol. 107, pp. 8618–8622.

    Article  CAS  Google Scholar 

  6. Smith, K.M., Poli, R., and Harvey, J.N., New. J. Chem., 2000, vol. 24, pp. 77–80.

    Article  CAS  Google Scholar 

  7. Koga, N. and Morokuma, K., Chem. Phys. Lett., 1985, vol. 119, pp. 371–374.

    Article  CAS  Google Scholar 

  8. Yarkony, D.R., J. Phys. Chem., 1993, vol. 97, pp. 4407–4412.

    Article  CAS  Google Scholar 

  9. Bearpark, M.J., Robb, M.A., and Schlegel, H.B., Chem. Phys. Lett., 1994, vol. 223, pp. 269–274.

    Article  CAS  Google Scholar 

  10. Farazdel, A. and Dupuis, M., J. Comp. Chem., 1991, vol. 12, pp. 276–282.

    Article  CAS  Google Scholar 

  11. Schmidt, M.W., Baldridge, K.K., Boatz, J.A., Elbert, S.T., Gordon, M.S., Jensen, J.J., Koseki, S., Matsunaga, N., Nguyen, K.A., Su, S., Windus, T.L., Dupuis, M., and Montgomery, J.A., J. Comput. Chem., 1993, vol. 14, pp. 1347–1363.

    Article  CAS  Google Scholar 

  12. Harvey, J.N. and Aschi, M., Phys. Chem. Chem. Phys., 1999, vol. 1, pp. 5555–5563.

    Article  CAS  Google Scholar 

  13. Minkin, V.I., Pichko, V.A., Abubikerova, I.A., and Simkin, B.Ya., J. Mol. Struct.: THEOCHEM, 1991, vol. 227, pp. 295–304.

    Article  Google Scholar 

  14. Kharabaev, N.N. and Minkin, V.I., Koord. Khim., 2003, vol. 29, no. 8, pp. 563–567.

    Google Scholar 

  15. Lo, J., M.H. and Klobukowski, M., Inorg. Chim. Acta, 2003, vol. 353, pp. 15–31.

    Article  CAS  Google Scholar 

  16. Everett, G.W., Jr. and Holm, R.H., J. Am. Chem. Soc., 1965, vol. 87, pp. 2117–2127.

    Article  CAS  Google Scholar 

  17. Minkin, V.I., Nivorozhkin, L.E., and Korobov, M.S., Usp. Khim., 1994, vol. 63, no. 4, pp. 303–326.

    CAS  Google Scholar 

  18. Garnovskii, A.D., Nivorozhkin, A.L., and Minkin, V.I., Coord. Chem. Rev., 1993, vol. 126, pp. 1–69.

    Article  CAS  Google Scholar 

  19. Everett, G.W., Jr. and Holm, R.H., Inorg. Chem., 1968, vol. 7, pp. 776–785.

    Article  CAS  Google Scholar 

  20. Sousa, S.F., Fernandes, P.A., and Ramos, M.J., J. Phys. Chem., A, 2007, vol. 111, pp. 10439–10452.

    Article  CAS  Google Scholar 

  21. Vosko, S.H., Wilk, L., and Nusair, M., Can. J. Phys., 1980, vol. 58, p. 1200.

    Article  CAS  Google Scholar 

  22. Becke, A.D., J. Chem. Phys., 1986, vol. 84, pp. 4524.

    Article  CAS  Google Scholar 

  23. Frisch, M.J., et al., GAUSSIAN 03, Revision D 01, Gaussian Inc., Wallingford, CT, 2004.

    Google Scholar 

  24. Minyaev, R.M., Usp. Khim., 1994, vol. 63, no. 11, pp. 939–961.

    CAS  Google Scholar 

  25. Harvey, J.N., Aschi, M., Schwarz, H., and Koch, W., Theor. Chem. Acc., 1998, vol. 99, pp. 95–99.

    CAS  Google Scholar 

  26. Starikov, A.G., Minyaev, R.M., and Minkin, V.I., Chem. Phys. Lett., 2008, vol. 459, pp. 27–32.

    Article  CAS  Google Scholar 

  27. Dohring, A., Goddard, R., Jolly, P.W., Kruger, C., and Polyakov, V.R., Inorg. Chem., 1997, vol. 36, p. 177.

    Article  Google Scholar 

  28. Zhu, Y.-Z., Liu, J.-Y., Li, Y.-S., and Tong, Y.-J., J. Organomet. Chem., 2004, vol. 689, pp. 1295–1303.

    Article  CAS  Google Scholar 

  29. Holm, R.H. and O’Connor, M.J., Progr. Inorg. Chem., 1971, vol. 14, pp. 241.

    Article  CAS  Google Scholar 

  30. Fox, M.R., Orioli, P.L., Lingafelter, E.C., and Sacconi, L., Acta Crystallogr., 1964, vol. 17, p. 1159.

    Article  CAS  Google Scholar 

  31. Everett, G.W., Jr. and Holm, R.H., J. Am. Chem. Soc., 1966, vol. 88, pp. 2442–2451.

    Article  CAS  Google Scholar 

  32. Wang, L.-C., Jang, H.-Y., Roh, Y., Lynch, V., Schultz, A.J., Wang, X., Krische, M.J., J. Am. Chem. Soc., 2002, vol. 124, p. 9448.

    Article  CAS  Google Scholar 

  33. Bourget-Merle, L., Lappert, M.F., and Severn, J.R., Chem. Rev., 2002, vol. 102, pp. 3031–3065.

    Article  CAS  Google Scholar 

  34. Bader, R.F.W., Atomy v molekulakh: kvantovaya teoriya (Atoms in Molecules. A Quantum Theory), Moscow: Mir, 2001, p. 532.

    Google Scholar 

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  1. Southern Scientific Center, Russian Academy of Sciences, pr. Stachek 194/2, Rostov-on-Don, 344090, Russia

    A. G. Starikov

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  1. A. G. Starikov
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Correspondence to A. G. Starikov.

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Original Russian Text © A.G. Starikov, 2009, published in Rossiiskii Khimicheskii Zhurnal, 2010, Vol. 53, No. 1, pp. 115–127.

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Starikov, A.G. Quantum-chemical study of intramolecular spin-forbidden rearrangements of the transition metal chelate complexes. Russ J Gen Chem 79, 2792–2806 (2009). https://doi.org/10.1134/S107036320912038X

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  • DOI: https://doi.org/10.1134/S107036320912038X

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