Skip to main content
SpringerLink
Log in

Circumambulatory Migrations of Arylazo Groups in Pentakis(methoxycarbonyl)- and Pentamethylcyclopentadienes

  • Published:
Russian Journal of Organic Chemistry Aims and scope Submit manuscript

Abstract

According to CAM–B3LYP/6-311++G(d,p) quantum chemical calculations, intramolecular migra­tion of the arylazo group in pentamethyl 5-(aryldiazenyl)cyclopentadiene-1,2,3,4,5-pentacarboxylates follows a dissociative mechanism through intermediate formation of tight ion pairs with a low energy barrier [ΔE≠ZPE = 14.0 and 16.5 kcal for Ar = C6H4NO2-4 and C6H3(NO2)2-2,4, respectively, in benzonitrile]. The arylazo group in 5-(aryldiazenyl)-1,2,3,4,5-pentamethylcyclopentadienes migrates via 1,5-sigmatropic shifts along the perimeter of the five-membered ring with exo orientation of the azo group with respect to that ring, and the migration process is characterized by significantly higher activation barriers [ΔE≠ZPE = 30.3 and 27.5 kcal/mol for Ar = C6H4NO2-4 and C6H3(NO2)2-2,4, respectively, in benzonitrile]. The calculated data are in good agreement with our previous results obtained by dynamic NMR.

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

Scheme
Fig. 1.
Fig. 2.
Fig. 3.
Fig. 4.
Scheme
Scheme
Scheme
Fig. 5.
Fig. 6.
Fig. 7.

CONFLICT OF INTEREST

The authors declare the absence of conflict of interest.

REFERENCES

  1. Shah, H.U.R., Ahmad, K., Naseem, H.A., Parveen, S., Ashfaq, M., Aziz, T., Shaheen, S., Babras, A., and Shahzad, A., J. Mol. Struct., 2021, vol. 1244, article ID 131181. https://doi.org/10.1016/j.molstruc.2021.131181

  2. Mahouche-Chergui, S., Gam-Derouich, S., Mange­ney, C., and Chehimi, M.M., Chem. Soc. Rev., 2011, vol. 40, p. 4143. https://doi.org/10.1039/C0CS00179A

    Article  CAS  PubMed  Google Scholar 

  3. Lindeman, S.V., Jay, K., and Kochi, J.K., Cryst Growth Des., 2004, vol. 4, p. 563. https://doi.org/10.1021/cg034218j

    Article  CAS  Google Scholar 

  4. Xia, Z., Leonardi, F., Gobbi, M., Liu, Y., Bellani, V., Liscio, A., Kovtun, A., Li, R., Feng, X., Orgiu, E., Samorì, P., Treossi, E., and Palermo, V., ACS Nano, 2016, vol. 10, p. 7125. https://doi.org/10.1021/acsnano.6b03278

    Article  CAS  PubMed  Google Scholar 

  5. Platonov, D.N., Okonnishnikova, G.P., Salikov, R.F., and Tomilov, Yu.V., Tetrahedron Lett., 2016, vol. 57, p. 4311. https://doi.org/10.1016/j.tetlet.2016.08.043

    Article  CAS  Google Scholar 

  6. Roglans, A., Pla-Quintana, A., and Moreno-Manas, M., Chem. Rev., 2006, vol. 106, p. 4622. https://doi.org/10.1021/cr0509861

    Article  CAS  PubMed  Google Scholar 

  7. Qiu, J., Tang, B., Ju, B., Xu, Y., and Zhang, S., Dyes Pigm., 2017, vol. 136, p. 63. https://doi.org/10.1016/j.dyepig.2016.08.026

    Article  CAS  Google Scholar 

  8. Mihelač, M., Siljanovska, A., and Košmrlj, J., Dyes Pigm., 2021, vol. 184, article ID 108726. https://doi.org/10.1016/j.dyepig.2020.108726

  9. Filimonov, V.D., Krasnokutskaya, E.A., Kassanova, A.Z., Fedorova, V.A., Stankevich, K.S., Naumov, N.G., Bondarev, A.A., and Kataeva, V.A., Eur. J. Org. Chem., 2019, vol. 2019, p. 665. https://doi.org/10.1002/ejoc.201800887

    Article  CAS  Google Scholar 

  10. Mikhailov, I.E., Dushenko, G.A., and Minkin, V.I., Russ. J. Org. Chem., 2021, vol. 57, p. 1757. https://doi.org/10.1134/S1070428021110014

    Article  CAS  Google Scholar 

  11. Dushenko, G.A., Mikhailov, I.E., Zschunke, A., and Minkin, V.I., Russ. J. Org. Chem., 1998, vol. 34, p. 1122.

    CAS  Google Scholar 

  12. Dushenko, G.A., Mikhailov, I.E., Skachkov, R.V., Zschunke, A., and Minkin, V.I., Russ. J. Org. Chem., 1996, vol. 32, p. 962.

    Google Scholar 

  13. Dushenko, G.A., Mikhailov, I.E., Skachkov, R.V., Klenkin, A.A., Divaeva, L.N., and Minkin, V.I., Zh. Org. Khim., 1994, vol. 30, p. 790.

    CAS  Google Scholar 

  14. Dushenko, G.A., Skachkov, R.V., Mikhailov, I.E., Divaeva, L.N., and Minkin, V.I., Zh. Org. Khim., 1994, vol. 30, p. 1076.

    CAS  Google Scholar 

  15. Minkin, V.I., Mikhailov, I.E., Dushenko, G.A., and Zschunke, A., Russ. Chem. Rev., 2003, vol. 72, p. 867. https://doi.org/10.1070/RC2003v072n10ABEH000848

    Article  CAS  Google Scholar 

  16. Dushenko, G.A., Mikhailov, I.E., and Minkin, V.I., Russ. J. Org. Chem., 2020, vol. 56, p. 1744. https://doi.org/10.1134/S1070428020100127

    Article  CAS  Google Scholar 

  17. Dushenko, G.A., Mikhailov, I.E., Mikhailova, O.I., Minyaev, R.M., and Minkin, V.I., Russ. Chem. Bull., Int. Ed., 2015, vol. 64, p. 2043. https://doi.org/10.1007/s11172-015-1115-z

    Article  CAS  Google Scholar 

  18. Dushenko, G.A., Mikhailov, I.E., Mikhailova, O.I., Minyaev, R.M., and Minkin, V.I., Russ. J. Gen. Chem., 2020, vol. 90, p. 161. https://doi.org/10.1134/S1070363220020012

    Article  CAS  Google Scholar 

  19. Shephard, A.C.G., Delon, A., Kelly, R.P., Guo, Z., Chevreux, S., Lemercier, G., Deacon, G.B., Dushen­ko, G.A., Jaroschik, F., and Junk, P.C., Aust. J. Chem., 2022, vol. 75, p. 746. https://doi.org/10.1071/CH21324

    Article  CAS  Google Scholar 

  20. Dushenko, G.A., Mikhailov, I.E., Mikhailova, O.I., Minyaev, R.M., and Minkin, V.I., Dokl. Chem., 2018, vol. 479, p. 53. https://doi.org/10.1134/S0012500818040067

    Article  CAS  Google Scholar 

  21. Gridnev, I.D. and Rosario, M.K.C., Organometallics, 2005, vol. 24, p. 4519. https://doi.org/10.1021/om050039i

    Article  CAS  Google Scholar 

  22. Bulo, R.E., Allaart, F., Ehlers, A.W., de Kanter, F.J.J., Schakel, M., Lutz, M., Spek, A.L., and Lammertsma, K., J. Am. Chem. Soc., 2006, vol. 128, p. 12169. https://doi.org/10.1021/ja0627895

    Article  CAS  PubMed  Google Scholar 

  23. Brydges, S., Harrington, L.E., and McGlinchey, M.J., Coord. Chem. Rev., 2002, vols. 233–234, p. 75. https://doi.org/10.1016/S0010-8545(02)00098-X

    Article  Google Scholar 

  24. Stefak, R., Sirven, A.M., Fukumoto, S., Nakagawa, H., and Rapenne, G., Coord. Chem. Rev., 2015, vol. 287, p. 79. https://doi.org/10.1016/j.ccr.2014.11.014

    Article  CAS  Google Scholar 

  25. Dushenko, G.A., Mikhailov, I.E., Mikhailova, O.I., Minyaev, R.M., and Minkin, V.I., Mendeleev Commun., 2015, vol. 25, p. 21. https://doi.org/10.1016/j.mencom.2015.01.007

    Article  CAS  Google Scholar 

  26. Mikhailov, I.E., Dushenko, G.A., Olekhnovich, L.P., and Minkin, V.I., Zh. Org. Khim., 1984, vol. 20, p. 2306.

    CAS  Google Scholar 

  27. Kompan, O.E., Antipin, M.Yu., Struchkov, Yu.T., Mi­khailov, I.E., Dushenko, G.A., Minkin, V.I., and Olekh­novich, L.P., Zh. Org. Khim., 1985, vol. 21, p. 2032.

    CAS  Google Scholar 

  28. Mikhailov, I.E., Dushenko, G.A., Minkin, V.I., Ustynyuk, Yu.A., and Olekhnovich, L.P., Zh. Org. Khim., 1984, vol. 20, p. 207.

    Google Scholar 

  29. Frisch, M.J., Trucks, G.W., Schlegel, H.B., Scu­seria, G.E., Robb, M.A., Cheeseman, J.R., Scalmani, G., Barone, V., Mennucci, B., Petersson, G.A., Naka­tsuji, H., Caricato, M., Li, X., Hratchian, H.P., Izmay­lov, A.F., Bloino, J., Zheng, G., Sonnenberg, J.L., Hada, M., Ehara, M., Toyota, K., Fukuda, R., Hasegawa, J., Ishida, M., Nakajima, T., Honda, Y., Kitao, O., Nakai, H., Vreven, T., Montgomery, J.A., Jr., Peralta, J.E., Ogliaro, F., Bearpark, M., Heyd, J.J., Brothers, E., Kudin, K.N., Staroverov, V.N., Keith, T., Kobayashi, R., Normand, J., Raghavachari, K., Ren­dell, A., Burant, J.C., Iyengar, S.S., Tomasi, J., Cossi, M., Rega, N., Millam, J.M., Klene, M., Knox, J.E., Cross, J.B., Bakken, V., Adamo, C., Jaramillo, J., Gomperts, R., Stratmann, R.E., Yazyev, O., Austin, A.J., Cammi, R., Pomelli, C., Ochterski, J.W., Martin, R.L., Morokuma, K., Zakrzewski, V.G., Voth, G.A., Salvador, P., Dannenberg, J.J., Dapprich, S., Daniels, A.D., Farkas, O., Foresman, J.B., Ortiz, J.V., Cioslowski, J., and Fox, D.J., Gaussian 09, Revision E.01, Wallingford CT, 2013.

Download references

Funding

This study was financially supported by the Ministry of Science and Higher Education of the Russian Federation in the framework of state assignment in the sphere of research activity (project no. FENW-2023-0017).

Author information

Authors and Affiliations

  1. Research Institute of Physical and Organic Chemistry, Southern Federal University, 344090, Rostov-on-Don, Russia

    G. A. Dushenko, I. E. Mikhailov & V. I. Minkin

Authors
  1. G. A. Dushenko
    View author publications

    You can also search for this author in PubMed Google Scholar

  2. I. E. Mikhailov
    View author publications

    You can also search for this author in PubMed Google Scholar

  3. V. I. Minkin
    View author publications

    You can also search for this author in PubMed Google Scholar

Corresponding author

Correspondence to G. A. Dushenko.

Additional information

Translated from Zhurnal Organicheskoi Khimii, 2023, Vol. 59, No. 9, pp. 1193–1208 https://doi.org/10.31857/S0514749223090094.

Publisher's Note. Pleiades Publishing remains neutral with regard to jurisdictional claims in published maps and institutional affiliations.

Rights and permissions

Reprints and permissions

About this article

Check for updates. Verify currency and authenticity via CrossMark

Cite this article

Dushenko, G.A., Mikhailov, I.E. & Minkin, V.I. Circumambulatory Migrations of Arylazo Groups in Pentakis(methoxycarbonyl)- and Pentamethylcyclopentadienes. Russ J Org Chem 59, 1523–1536 (2023). https://doi.org/10.1134/S1070428023090099

Download citation

  • Received:

  • Revised:

  • Accepted:

  • Published:

  • Issue Date:

  • DOI: https://doi.org/10.1134/S1070428023090099

Keywords:

Search

Navigation