New approaches to assessing the stability of carbenes

Authors

  • N. I. Korotkikh Institute of Organic Chemistry of the National Academy of Sciences of Ukraine, Ukraine
  • G. F. Rayenko Institute of Physical Organic and Coal Chemistry of the National Academy of Sciences of Ukraine, Ukraine
  • V. Sh. Saberov Institute of Organic Chemistry of the National Academy of Sciences of Ukraine, Ukraine
  • V. I. Yenya Institute of Organic Chemistry of the National Academy of Sciences of Ukraine, Ukraine
  • O. P. Shvaika Institute of Physical Organic and Coal Chemistry of the National Academy of Sciences of Ukraine, Ukraine

DOI:

https://doi.org/10.24959/ophcj.19.183372

Keywords:

carbenes, general and cyclic stabilization energies, electronic and steric parameter of substituents

Abstract

Carbenes are known to be highly reactive compounds, which can, in turn, spontaneously transform to dimers and products of rearrangements. Therefore, the question about the estimation of stability of carbenes is fundamental in the design of compounds for their subsequent synthesis and application.
Aim. To consider the known methods for assessing the stability and stabilization of carbenes, first of all, created by the authors of the article, and show their possibilities in predicting the properties of carbenes.
Materials and methods. The study was performed using the DFT method (B3LYP5, 6-311G**, RHF) to estimate the stabilization energies, and the DFT (B3LYP5, 6-31G, RHF) to obtain dimerization energies.
Results and discussion. The ways of solving the problem of stability of carbenes by the methods of quantum chemistry are discussed, in particular the application of new criteria for the stabilization of cyclic compounds – energies of the general and cyclic stabilization, energies of non-aromatic conjugations. To assess the possibility of isolating compounds the study of standard dimerization enthalpies (according to the ESP electronic and steric parameter proposed) for different classes of heterocyclic carbenes has been performed taking into account conformational factors. The scale of substituent effects on the stability of carbenes has been developed. It has been shown that sterically shielding substituents cause not only the kinetic stabilization, but also the thermodynamic one. The skeletons of the molecules have been estimated for their degree of influence on the stability of the compounds.
Conclusions. The parameters proposed for assessing the energies of the total and cyclic stabilization of carbenes, the dimerization energies of complex carbenes (electronic and steric parameter) allow identifying the most stable structures in the design of compounds for their subsequent synthesis and application.

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References

  1. Enders, D., Niemeier, O., Henseler, A. (2007). Organocatalysis by N-heterocyclic carbenes. Chemical Reviews, 107 (12), 5606–5655. https://doi.org/10.1021/cr068372z
  2. Korotkikh, N. I., Shvaika, O. P. (2013). Karbenovyi ta carbenocomplexnyi catalyz organichnykh reakcii. Donetsk: DonNU, 372.
  3. Korotkikh, N., Shvaika, O. (2015). Organic reactions catalysis by carbenes and metal carbene complexes. LAP Lambert Academic Publishing, 385.
  4. Martin, D., Melaimi, M., Soleilhavoup, M., Bertrand, G. (2011). A brief survey of our contribution to stable carbene chemistry. Organometallics, 30 (20), 5304–5313. https://doi.org/10.1021/om200650x
  5. Jahnke, M. C., Ekkehardt Hahn, F. (2011). Chapter 1. Introduction to N-heterocyclic carbenes: synthesis and stereoelectronic parameters. N-Heterocyclic carbenes: from laboratory curiosities to efficient synthetic tools. Royal Society of Chemistry, 1–41. doi:10.1039/9781849732161-00001
  6. Korotkikh, N. I., Cowley, A. H., Clyburne, J. A. C., Robertson, K. N., Saberov, V. Sh., Glinyanaya, N. V., Rayenko, G. F., Shvaika, O. P. (2017). Synthesis and properties of heteroaromatic carbenes of the imidazole and triazole series and their fused analogues. Arkivoc, I, 257–355. https://doi.org/10.24820/ark.5550190.p010.110
  8. Nyiri, K., Veszprémi, T. (2009). On the stability of six-membered-ring carbenes and silylenes. Organometallics, 28 (20), 5909–5914. https://doi.org/10.1021/om900587m
  9. Kelemen, Z., Hollóczki, O., Oláh, J., Nyulászi, L. (2013). Oxazol-2-ylidenes. A new class of stable carbenes? RSC Advances, 3 (21), 7970–7978. https://doi.org/10.1039/c3ra41177j
  10. Heinemann, C., Müller, T., Apeloig, Y., Schwarz, H. (1996). On the question of stability, conjugation, and “aromaticity” in imidazol-2-ylidenes and their silicon analogs. Journal of the American Chemical Society, 118 (8), 2023–2038. https://doi.org/10.1021/ja9523294
  11. Boehme, C., Frenking, G. (1996). Electronic structure of stable carbenes, silylenes, and germylenes. Journal of the American Chemical Society, 118 (8), 2039–2046. https://doi.org/10.1021/ja9527075
  12. Vasiliu, M., Peterson, K. A., Arduengo, A. J., Dixon, D. A. (2017). Characterization of carbenes via hydrogenation energies, stability, and reactivity – what’s in a name? Chemistry – A European Journal, 23 (69), 17556–17565. https://doi.org/10.1002/chem.201703539
  13. Carter, E. A., Goddard, W. A. (1986). Relation between singlet-triplet gaps and bond energies. The Journal of Physical Chemistry, 90 (6), 998–1001. https://doi.org/10.1021/j100278a006
  14. Nyulászi, L., Veszpre´mi, T., Forró, A. (2000). Stabilized carbenes do not dimerize. Physical Chemistry Chemical Physics, 2 (14), 3127–3129. https://doi.org/10.1039/b003588m
  15. Poater, A., Ragone, F., Giudice, S., Costabile, C., Dorta, R., Nolan, S. P., Cavallo, L. (2008). Thermodynamics of N-heterocyclic carbene dimerization: the balance of sterics and electronics. Organometallics, 27 (12), 2679–2681. https://doi.org/10.1021/om8001119
  16. Rezaee, N., Ahmadi, A., Kassaee, M. Z. (2016). Nucleophilicity of normal and abnormal N-heterocyclic carbenes at DFT: steric effects on tetrazole-5-ylidenes. RSC Advances, 6 (16), 13224–13233. https://doi.org/10.1039/c5ra21247b
  17. Jolly, P. I., Zhou, S., Thomson, D. W., Garnier, J., Parkinson, J. A., Tuttle, T., Murphy, J. A. (2012). Imidazole-derived carbenes and their elusive tetraazafulvalene dimers. Chemical Science, 3 (5), 1675–1679. https://doi.org/10.1039/c2sc20054f
  18. Suzuki, Y., Onoa, R. J., Ueda, M., Bielawski, C. W. (2013). N-Heterocyclic carbene enabled synthesis of conjugated polymers. European Polymer Journal, 49 (12), 4276–4280. https://doi.org/10.1016/j.eurpolymj.2013.09.023
  19. Wu, C.-S., Su, M.-D. (2012). Reactivity for boryl(phosphino)carbenyl carbene analogues with group 14 elements (C, Si, Ge, Sb, and Pb) as a heteroatom: a theoretical study. Dalton Transactions, 41 (11), 3253–3265. https://doi.org/10.1039/c2dt11464j
  20. Pozharskii, A. F. (1985). Heteroaromaticity (review). Chemistry of Heterocyclic Compounds, 21 (7), 717–749. https://doi.org/10.1007/BF00519137
  21. Krygowski, T. M., Cyrañski, M. K., Czarnocki, Z., Häfelinger, G., Katritzky, A. R. (2000). Aromaticity: a theoretical concept of immense practical importance. Tetrahedron, 56 (13), 1783–1796. https://doi.org/10.1016/s0040-4020(99)00979-5
  22. Korotkikh, M., Kiselyov, A., Rayenko, G., Opeida, I., Shvaika, O. (2008). Comparative estimation of stabilization energies for aromatic compounds by enthalpies of isodesmic reactions. Proceedings of the Shevchenko Scientific Society: Chemical sciences, 21, 7–63.
  23. Korotkikh, M., Rayenko, H., Saberov, V., Shvaika, O. (2019). Enerhii dymeryzatsii yak vahomyi faktor stabilnosti karbeniv. I. Imidazol-2-ilideny. Proceedings of the Shevchenko Scientific Society: Chemical sciences, 56, 7–22.
  24. Korotkikh, M., Rayenko, H., Saberov, V., Shvaika, O. (2019). Enerhii dymeryzatsii yak vahomyi faktor stabilnosti karbeniv. II. N,N’-dyzamishcheni azolilideny ta systemy z pidvyshchenoiu elektronodonornistiu. Proceedings of the Shevchenko Scientific Society: Chemical sciences, 56, 23–34.
  25. Korotkikh, M., Rayenko, H., Saberov, V., Shvaika, O. (2019). Enerhii dymeryzatsii yak vahomyi faktor stabilnosti karbeniv. III. Kondensovani ta novitni vysokoelektronodonorni systemy. Proceedings of the Shevchenko Scientific Society: Chemical sciences, 56, 35–44.
  26. Wanzlick, H. W. (1962). Aspects of nucleophilic carbene chemistry. Angewandte Chemie International Edition in English, 1 (2), 75–80. https://doi.org/10.1002/anie.196200751
  27. Wiberg, N. (1968). Tetraaminoethylenes as strong electron donors. Angewandte Chemie International Edition in English, 7 (10), 766–779. https://doi.org/10.1002/anie.196807661
  28. Çetinkaya, E., Hitchcock, P. B., Küçükbay, H., Lappert, M. F., Al-Juaid, S. (1994). Carbene complexes. XXIV. Preparation and characterization of two enetetramine-derived carbenerhodium(I) chloride complexes RhCI(LR)3 and [RhCl(COD)LR] (LR = dCN(Me)Cu(CH)4CNMe-o) and the preparation and X-ray structures of the enetetramine L2R and its salt [L2R][BF4]. Journal of Organometallic Chemistry, 481 (1), 89–95. https://doi.org/10.1016/0022-328x(94)85013-5
  29. Denk, M. K., Hatano, K., Ma, M. (1999). Nucleophilic carbenes and the Wanzlick equilibrium: a reinvestigation. Tetrahedron Letters, 40 (11), 2057–2060. https://doi.org/10.1016/s0040-4039(99)00164-1

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Published

2019-11-14

How to Cite

(1)
Korotkikh, N. I.; Rayenko, G. F.; Saberov, V. S.; Yenya, V. I.; Shvaika, O. P. New Approaches to Assessing the Stability of Carbenes. J. Org. Pharm. Chem. 2019, 17, 18-27.

Issue

Vol. 17 No. 4(68) (2019)

Section

Original Researches

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