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Prototropic tautomerism of the addition products of N-heterocyclic carbenes to CO2, CS2, and COS

  • Ibon AlkortaEmail author
  • José Elguero
Original Research

Abstract

The energies of 62 minima and 6 transition states have been calculated with the M06-2x functional and the aug-cc-pVDZ basis set. They correspond to carbenes and neutral molecules related to the products obtained by addition of N-heterocyclic carbenes (NHCs) to CO2, CS2, and COS. The NHCs belong to two “classical” NHCs (imidazoles and benzimidazoles) and one “remote” NHC (pyrazole). Several of these structures in the same series are related by prototropic tautomerism. To compare these calculated energies with experimental X-ray structures, solvation effects by water, calculated with a continuous model (PCM), as well as some dihydrates and dimers, have also been calculated.

Keywords

NHC Imidazoles Benzimidazoles Pyrazoles Carboxylic acids X-ray structures 

Notes

Acknowledgments

The authors would like to thank the CTI (CSIC) for their continued computational support.

Funding information

This work was carried out with the financial support from the Ministerio de Ciencia, Innovación y Universidades (Project No. PGC2018-094644-B-C22) and Comunidad Autónoma de Madrid (P2018/EMT-4329 AIRTEC-CM).

Compliance with ethical standards

Conflict of interest

The authors declare that they have no conflict of interest.

Supplementary material

11224_2019_1381_MOESM1_ESM.docx (45 kb)
ESM 1 (DOCX 45 kb)

References

  1. 1.
    Díez-González S (ed) (2011) N-Heterocyclic carbenes: from laboratory curiosities to efficient synthetic tools. Royal Society of Chemistry, LondonGoogle Scholar
  2. 2.
    Nolan SP (ed) (2014) N-Heterocyclic carbenes: effective tools for organometallic synthesis. Wiley-VCH, WeinheimGoogle Scholar
  3. 3.
    Kirchner B (ed) (2010) Ionic Liquids. Topics Curr Chem, vol 290. Google Scholar
  4. 4.
    Zhang S, Wang J, Lu X, Eds ZQ (2014) Structure and interactions of ionic liquids. Struct Bond:151Google Scholar
  5. 5.
    Erker G, Stephan DW (2013) Frustrated Lewis Pairs I. Topics Curr Chem:332Google Scholar
  6. 6.
    Erker G, Stephan DW (2013) Frustrated Lewis Pairs II. Topics Curr Chem:334Google Scholar
  7. 7.
    Möricke J, Rehwinkel F, Danelzik T, Daniluc CG, Wibbeling B, Kehr G, Erker G (2019). Tetrahedron 75:571–579CrossRefGoogle Scholar
  8. 8.
    Arduengo AJ, Harlow RL, Kline M (1991). J Am Chem Soc 113:361–363CrossRefGoogle Scholar
  9. 9.
    Gronert S, Keefe JR, O'Ferrall RAM (2014) Carbene stability in contemporary carbene chemistry. In: Moss RA, Doyle MP (eds). Wiley, HobokenGoogle Scholar
  10. 10.
    Kleinpeter E, Koch A (2019). Tetrahedron 75:1548–1554CrossRefGoogle Scholar
  11. 11.
    Tonner R, Heydenrych G, Frenking G (2007). Chem Asian J 2:1555–1567CrossRefGoogle Scholar
  12. 12.
    Amyes TL, Diver ST, Richard JP, Rivas FM, Toth K (2004). J Am Chem Soc 126:4366–4374CrossRefGoogle Scholar
  13. 13.
    Magill AM, Yates BF (2004). Austr J Chem 57:1205–1210CrossRefGoogle Scholar
  14. 14.
    Ajitha MJ, Suresh CH (2012). J Org Chem 77:1087–1094CrossRefGoogle Scholar
  15. 15.
    Delaude L (2009). Eur J Inorg Chem:1681–1699Google Scholar
  16. 16.
    Schofield K, Grimmett MR, Keene BRT (1976) The azoles. Cambridge University Press, CambridgeGoogle Scholar
  17. 17.
    Kelemen Z, Péter-Szabó B, Székely E, Hollócczki O, Firaha DS, Kirchner B, Nagy J, Nyulászi L (2014). Chem Eur J 20:13002–13008CrossRefGoogle Scholar
  18. 18.
    Baek KY, Jo JH, Moon JH, Yoon J, Lee JY (2015). J Org Chem 80:1878–1886CrossRefGoogle Scholar
  19. 19.
    Katritzky AR (1955). Chem Ind:521–522Google Scholar
  20. 20.
    Ollis WD, Stanforth SP, Ramsden CA (1985). Tetrahedron 41:2239–2329CrossRefGoogle Scholar
  21. 21.
    Potts KT, Murphy PM, DeLuca MR, Kuehnling WR (1988). J Org Chem 53:2898–2910CrossRefGoogle Scholar
  22. 22.
    Pidlypnyi N, Namyslo JC, Drafz MHH, Nieger M, Schmidt A (2013). J Org Chem 78:1070–1079CrossRefGoogle Scholar
  23. 23.
    Schmidt A, Wiechmann S, Freese T (2013). Arkivoc i:424–469Google Scholar
  24. 24.
    Cowgill RW, Clark WM (1952). J Biol Chem 198:33–61Google Scholar
  25. 25.
    Kuhn N, Steimann M, Weyers G (1999). Z Naturforsch 54b:427–433CrossRefGoogle Scholar
  26. 26.
    Zhou H, Zhang WZ, Liu CH, Qu JP, Lu XB (2008). J Org Chem 73:8039–8044CrossRefGoogle Scholar
  27. 27.
    Kayaki Y, Yamamoto M, Ikariya T (2009). Angew Chem Int Ed 48:4194–4197CrossRefGoogle Scholar
  28. 28.
    Gu L, Zhang Y (2010). J Am Chem Soc 132:914–915CrossRefGoogle Scholar
  29. 29.
    Van Ausdall BR, Glass JL, Wiggins KM, Aarif AM, Louie J (2009). J Org Chem 74:7935–7942CrossRefGoogle Scholar
  30. 30.
    Liu M, Nieger M, Schmidt A (2015). Chem Commun 51:477–479CrossRefGoogle Scholar
  31. 31.
    Li W, Huang D, Lv Y (2014). RSC Adv 4:17236–17244CrossRefGoogle Scholar
  32. 32.
    Zhou Q, Li Y (2015). J Am Chem Soc 137:10182–10189CrossRefGoogle Scholar
  33. 33.
    Holbrey JD, Reichert WM, Tkatchenko I, Bouajila E, Walter O, Tommasi I, Rogers RD (2003). Chem Commun 8:29Google Scholar
  34. 34.
    Del Bene JE, Alkorta I, Elguero J (2017). J Phys Chem A 121:4039–4047CrossRefGoogle Scholar
  35. 35.
    Del Bene JE, Alkorta I, Elguero J (2017). J Phys Chem A 121:8136–8146CrossRefGoogle Scholar
  36. 36.
    Alkorta I, Montero-Campillo MM, Elguero J (2017). Chem Eur J 23:10604–10609CrossRefGoogle Scholar
  37. 37.
    Del Bene JE, Alkorta I, Elguero J (2018). Molecules 23:906CrossRefGoogle Scholar
  38. 38.
    Montero-Campillo MM, Alkorta I, Elguero J (2018). Phys Chem Chem Phys 20:19552–19559Google Scholar
  39. 39.
    Zhao Y, Truhlar DG (2006). Theor Chem Accounts 120:215–241CrossRefGoogle Scholar
  40. 40.
    Dunning TH (1989). J Chem Phys 90:1007–1023CrossRefGoogle Scholar
  41. 41.
    Frisch MJ, Trucks GW, Schlegel HB, Scuseria GE, Robb MA, Cheeseman JR, Scalmani G, Barone V, Petersson GA, Nakatsuji H, Li X, Caricato M, Marenich AV, Bloino J, Janesko BG, Gomperts R, Mennucci B, Hratchian HP, Ortiz JV, Izmaylov AF, Sonnenberg JL, Williams-Young D, Ding F, Lipparini F, Egidi F, Goings J, Peng B, Petrone A, Henderson T, Ranasinghe D, Zakrzewski VG, Gao J, Rega N, Zheng G, Liang W, Hada M, Ehara M, Toyota K, Fukuda R, Hasegawa J, Ishida M, Nakajima T, Honda Y, Kitao O, Nakai H, Vreven T, Throssell K, Montgomery JA, Peralta JE, Ogliaro F, Bearpark MJ, Heyd JJ, Brothers EN, Kudin KN, Staroverov VN, Keith TA, Kobayashi R, Normand J, Raghavachari K, Rendell AP, Burant JC, Iyengar SS, Tomasi J, Cossi M, Millam JM, Klene M, Adamo C, Cammi R, Ochterski JW, Martin RL, Morokuma K, Farkas O, Foresman JB, Fox DJ (2016) Gaussian 16, Revision B.01. Gaussian, Inc, Wallingford CTGoogle Scholar
  42. 42.
    Groom CR, Bruno IJ, Lighfoot MP, Ward SC (2016) The Cambridge Structural Database, CSD Version 5.40, Feb. 2019 update. Acta Crystallogr Sect B 72:171–179CrossRefGoogle Scholar
  43. 43.
    Campillo N, Alkorta I, Páez JA, Goya P (1998). J Chem Soc Perkin Trans 2:1889–1892CrossRefGoogle Scholar
  44. 44.
    Gu J, Leszczynski J (1999). J Phys Chem 103:2744–2750CrossRefGoogle Scholar
  45. 45.
    Trujillo C, Sánchez-Sanz G, Alkorta I, Elguero J (2015). ChemPhysChem 16:2140–2150CrossRefGoogle Scholar
  46. 46.
    Oziminski WP (2016). Struct Chem 27:1845–1854CrossRefGoogle Scholar
  47. 47.
    Delaere D, Raspoet G, Nguyen MT (1999). J Phys Chem A 103:171–177CrossRefGoogle Scholar
  48. 48.
    Elguero J, Katritzky AR, Denisko O (2000). Adv Heterocycl Chem 76:1–84CrossRefGoogle Scholar

Copyright information

© Springer Science+Business Media, LLC, part of Springer Nature 2019

Authors and Affiliations

  1. 1.Instituto de Química Médica, CSICMadridSpain

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