Skip to main content
SpringerLink
Log in

Synthesis, Crystal Structure, and Properties of Phenylsilicon(IV) Bis-catecholate Complexes

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

Abstract

A series of anionic phenylsilicon(IV) bis-catecholate complexes, where (Cat1)– = catecholate, (Cat2)– = 3,4,5,6-tetrabromocatecholate, (Cat3)– = 4-cyanocatecholate, (Cat4)– = 4-nitrocatecholate, (Cat5)– = 3-fluorocatecholate, and (Cat6)– = 4,5-dibromocatecholate, were prepared by the reaction of trimethoxyphenylsilane with two equivalents of catechol or its derivatives containing electron-withdrawing substituents in the benzene ring in the presence of dicyclohexylamine. The complexes were characterized by IR spectra and 1H, 13C, and 29Si NMR spectra, voltammetry, and ESR. The heteroligand anionic phenylsilicon(IV) complexes crystallized from solutions as salts (Chex2NH2)[PhSi(Cat1)2] (I), (Chex2NH2)-[PhSi(Cat2)2]·0.5C6H14 (II), (Chex2NH2)[PhSi(Cat3)2]·2C6H6 (III), (Chex2NH2)[PhSi(Cat4)2]· H2O (IV), (Chex2NH2)[PhSi(Cat5)2] (V), and (Chex2NH2)[PhSi(Cat6)2] (VI) (Chex2\({\text{NH}}_{2}^{ + }\) = dicyclohexylammonium). The composition and structure of the products were confirmed by X-ray diffraction data (CCDC nos. 2150293–2150297 for I–V, respectively). The effect of substituent in the benzene ring on the electronic structure of the anion was studied by PBE0/6-311G(d,p) quantum chemical calculations with allowance for non-specific solvation (PCM model). The oxidation potentials of II–VI were measured; radical formation upon electrochemical oxidation and reduction was observed for II.

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

Fig. 1.
Fig. 2.
Fig. 3.
Fig. 4.
Fig. 5.
Fig. 6.
Fig. 7.
Fig. 8.
Fig. 9.

Similar content being viewed by others

REFERENCES

  1. Corce, V., Chamoreau, L.-M., Derat, E., et al., Angew. Chem., Int. Ed. Engl., 2015, vol. 54, no. 39, p. 11414. https://doi.org/10.1002/anie.201504963

    Article  CAS  Google Scholar 

  2. Raynor, K.D., May, G.D., Bandarage, U.K., et al., Org. Chem., 2018, vol. 83, no. 3, p. 1551. https://doi.org/10.1021/acs.joc.7b02680

  3. Lin, K., Wiles, R.J., Kelly, C.B., et al., ACS Catal., 2017, vol. 7, no. 8, p. 5129. https://doi.org/10.1021/acscatal.7b01773

    Article  CAS  PubMed  PubMed Central  Google Scholar 

  4. Levernier, E., Corcé, V., Rakotoarison, L.-M., et al., Org. Chem. Front., 2019, vol. 6, no. 9, p. 1378. https://doi.org/10.1039/C9QO00092E

    Article  CAS  Google Scholar 

  5. Lévêque, C., Chenneberg, L., Corcé, V., et al., Org. Chem. Front., 2016, vol. 3, no. 4, p. 462. https://doi.org/10.1039/C6QO00014B

    Article  CAS  Google Scholar 

  6. Patel, N.R., Kelly, C.B., Siegenfeld, A.P., et al., ACS Catal., 2017, vol. 7, no. 3, p. 1766. https://doi.org/10.1021/acscatal.6b03665

    Article  CAS  PubMed  PubMed Central  Google Scholar 

  7. Cartier, A., Levernier, E., Corcé, V., et al., Angew. Chem., 2019, vol. 131, no. 6, p. 1803. https://doi.org/10.1002/ange.201811858

    Article  Google Scholar 

  8. Levernier, E., Jaouadi, K., Zhang, H.-R., et al., Chem.-Eur. J., 2021, vol. 27, no. 34, p. 8782. https://doi.org/10.1002/chem.202100453

    Article  CAS  PubMed  Google Scholar 

  9. Blessing, R.H., Acta Crystallogr., Sect. A: Found. Crystallogr., 1995, vol. A51, no. 1, p. 33. https://doi.org/10.1107/S0108767394005726

    Article  CAS  Google Scholar 

  10. APEX3 Suite for Crystallographic Software — Single Crystal X-ray Diffraction, Bruker AXS, 2014.

  11. Dolomanov, O.V., Bourhis, L.J., Gildea, R.J., et al., J. Appl. Crystallogr., 2009, vol. 42, no. 2, p. 339. https://doi.org/10.1107/S0021889808042726

    Article  CAS  Google Scholar 

  12. Sheldrick, G.M., Acta Crystallogr., Sect. A: Cryst. Adv., 2015, vol. 71, no. 1, p. 3. https://doi.org/10.1107/S2053273314026370

    Article  CAS  Google Scholar 

  13. Sheldrick, G.M., Acta Crystallogr., Sect. C: Struct. Chem., 2015, vol. 71, no. 1, p. 3. https://doi.org/10.1107/S2053229614024218

    Article  CAS  Google Scholar 

  14. Krylov, A.I. and Gill, P.M.W., WIREs Comput. Mol. Sci., 2013, vol. 3, no. 3, p. 317. https://doi.org/10.1002/wcms.1122

  15. Epifanovsky, E., Gilbert, A.T.B., Feng, X., et al., J. Chem. Phys., 2021, vol. 155, no. 8, p. 084801. https://doi.org/10.1063/5.0055522

    Article  CAS  PubMed  Google Scholar 

  16. Neugebauer, H., Bohle, F., Bursch, M., et al., J. Phys. Chem. A, 2020, vol. 124, no. 35, p. 7166. https://doi.org/10.1021/acs.jpca.0c05052

    Article  CAS  PubMed  Google Scholar 

  17. Lu, T. and Chen, F., J. Comput. Chem., 2012, vol. 33, no. 5, p. 580. https://doi.org/10.1002/jcc.22885

    Article  CAS  PubMed  Google Scholar 

  18. Humphrey, W., Dalke, A., and Schulten, K., J. Mol. Graph., 1996, vol. 14, no. 1, p. 33. https://doi.org/10.1016/0263-7855(96)00018-5

    Article  CAS  PubMed  Google Scholar 

  19. Boer, F.P., Flynn, J.J., and Turley, J.W., J. Am. Chem. Soc., 1968, vol. 90, no. 25, p. 6973. https://doi.org/10.1021/ja01027a014

    Article  CAS  Google Scholar 

  20. Holmes, R.R., Day, R.O., Chandrasekhar, V., et al., Inorg. Chem., 1985, vol. 24, no. 13, p. 2009. https://doi.org/10.1021/ic00207a012

    Article  CAS  Google Scholar 

  21. Holmes, R.R., Day, R.O., Harland, J.J., et al., Organometallics, 1984, vol. 3, no. 3, p. 341. https://doi.org/10.1021/om00081a001

    Article  CAS  Google Scholar 

  22. Holmes, R.R. and Deiters, J.A., J. Am. Chem. Soc., 1977, vol. 99, no. 10, p. 3318. https://doi.org/10.1021/ja00452a021

    Article  CAS  Google Scholar 

  23. Korlyukov, A.A., Usp. Khim., 2015, vol. 84, no. 4, p. 422.

    Article  CAS  Google Scholar 

  24. Kramarova, E.P., Volodin, A.D., Negrebetsky, V.V., et al., Molecules, 2021, vol. 26, no. 12, p. 3548. https://doi.org/10.3390/molecules26123548

    Article  CAS  PubMed  PubMed Central  Google Scholar 

  25. Korlyukov, A.A., Shipov, A.G., Kramarova, E.P., et al., Izv. Akad. Nauk. Ser. Khim., 2008, no. 10, p. 2055.

  26. O’Keeffe, M., Peskov, M.A., Ramsden, S.J., et al., Acc. Chem. Res., 2008, vol. 41, no. 12, p. 1782. https://doi.org/10.1021/ar800124u

    Article  CAS  PubMed  Google Scholar 

  27. Politzer, P. and Murray, J.S., Theoretical and Computational Chemistry, Chapter 8: The Averag Local Ionization Energy: Concepts and Applications, Toro-Labbe, A., Ed., 2007, vol. 19, p. 119. https://doi.org/10.1016/S1380-7323(07)80009-4

  28. Namazian, M., Lin, C.Y., and Coote, M.L., J. Chem. Theory Comput., 2010, vol. 6, no. 9, p. 2721. https://doi.org/10.1021/ct1003252

    Article  CAS  PubMed  Google Scholar 

Download references

ACKNOWLEDGMENTS

Elemental analysis, X-ray diffraction studies, and recording of NMR and IR spectra were supported by the Ministry of Science and Higher Education of the Russian Federation and performed using research equipment of the Molecular Structure Investigation Center of the Nesmeyanov Institute of Organoelement Compounds, Russian Academy of Sciences. P.A. Buikin and A.A. Korlyukov are grateful to the Interdepartmental Supercomputer Center, Russian Academy of Sciences, for providing access to computational resources and software.

Funding

This study was supported by the Russian Foundation for Basic Research (grant no. 19-29-08021).

Author information

Authors and Affiliations

  1. Pirogov Russian National Research Medical University, Moscow, Russia

    E. P. Kramarova, V. V. Negrebetskii & A. A. Korlyukov

  2. Nesmeyanov Institute of Organoelement Compounds, Russian Academy of Sciences, Moscow, Russia

    A. D. Volodin, P. A. Buikin, T. M. Aliev, A. A. Korlyukov & A. V. Vologzhanina

  3. Kurnakov Institute of General and Inorganic Chemistry, Russian Academy of Sciences, Moscow, Russia

    P. A. Buikin

  4. Zelinsky Institute of Organic Chemistry, Russian Academy of Sciences, Moscow, Russia

    A. V. Lalov & R. A. Novikov

Authors
  1. E. P. Kramarova
    View author publications

    You can also search for this author in PubMed Google Scholar

  2. V. V. Negrebetskii
    View author publications

    You can also search for this author in PubMed Google Scholar

  3. A. D. Volodin
    View author publications

    You can also search for this author in PubMed Google Scholar

  4. P. A. Buikin
    View author publications

    You can also search for this author in PubMed Google Scholar

  5. A. V. Lalov
    View author publications

    You can also search for this author in PubMed Google Scholar

  6. R. A. Novikov
    View author publications

    You can also search for this author in PubMed Google Scholar

  7. T. M. Aliev
    View author publications

    You can also search for this author in PubMed Google Scholar

  8. A. A. Korlyukov
    View author publications

    You can also search for this author in PubMed Google Scholar

  9. A. V. Vologzhanina
    View author publications

    You can also search for this author in PubMed Google Scholar

Corresponding author

Correspondence to A. V. Vologzhanina.

Ethics declarations

The authors declare that they have no conflicts of interest.

Additional information

Dedicated to Academician Yu.A. Zolotov in the year of his 90th birthday

Translated by Z. Svitanko

Supplementary Information

Rights and permissions

Reprints and permissions

About this article

Check for updates. Verify currency and authenticity via CrossMark

Cite this article

Kramarova, E.P., Negrebetskii, V.V., Volodin, A.D. et al. Synthesis, Crystal Structure, and Properties of Phenylsilicon(IV) Bis-catecholate Complexes. Russ J Coord Chem 48, 647–658 (2022). https://doi.org/10.1134/S1070328422090019

Download citation

  • Received:

  • Revised:

  • Accepted:

  • Published:

  • Issue Date:

  • DOI: https://doi.org/10.1134/S1070328422090019

Keywords:

Search

Navigation