Skip to main content
SpringerLink
Log in

Structure elucidation of pentakis(methoxycarbonyl)- and amidinyltetrakis(methoxycarbonyl)cyclopentadienyl complexes of gold(I) by quantum chemistry methods

  • Full Articles
  • Published:
Russian Chemical Bulletin Aims and scope

Abstract

Density functional CAM-B3LYP/6-311++G(d,p)/SDD quantum chemical calculations of a gold(I) complex with the pentakis(methoxycarbonyl)cyclopentadienyl ligand Ph3PAu[C5(CO2Me)5] and gold(I) complexes with polydentate amidinyltetrakis(methoxycarbonyl)cyclopentadienyl ligands Ph3PAu[N(Ar)C(Ar’)N(Ar)C5(CO2Me)4] were carried out. It was shown that the former system, where the Au atom is bonded to the C(sp3) atom of the cyclopentadiene ring and additionally coordinated by two neighboring ring carbon atoms, exhibits fluxional behavior due to rapid 1,5-sigmatropic shifts of the AuPPh3 group along the perimeter of the five-membered ring occurring with an energy barrier (ΔG≠298 K) of 5.1 kcal mol−1. Contrary to this, all other gold(I) complexes are more stable as ylide isomers, where the gold atom is bonded to the terminal nitrogen atom of the amidinium fragment and additionally coordinated by the π-system of the cyclopentadiene ring. According to the CAM-B3LYP/6-311G(d,p)/SDD calculations, alternative isomers, in which the gold atom is bonded to the carbon atom of the cyclopentadiene ring or to the oxygen atom of the methoxycarbonyl substituent, are much less stable (ΔEZPE = = 12.8−20.0 kcal mol−1).

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

Similar content being viewed by others

References

  1. N. Mirzadeh, S. H. Privér, A. J. Blake, H. Schmidbaur, S. K. Bhargava, Chem. Rev., 2020, 120, 7551; DOI: https://doi.org/10.1021/acs.chemrev.9b00816.

    Article  CAS  Google Scholar 

  2. N. Mirzadeh, T. S. Reddy, S. K. Bhargava, Coord. Chem. Rev., 2019, 388, 343; DOI: https://doi.org/10.1016/j.ccr.2019.02.027.

    Article  CAS  Google Scholar 

  3. V. W.-W. Yam, E. C.-C. Cheng, Chem. Soc. Rev., 2008, 37, 1806; DOI: https://doi.org/10.1039/b708615f.

    Article  CAS  Google Scholar 

  4. V. V. Vysotsky, A. S. Dmitriev, I. A. Mikhailova, K. F. Chernyshova, O. V. Souvorova, A. A. Revina, Russ. Chem. Bull., 2020, 69, 32; DOI: https://doi.org/10.1007/s11172-020-2720-z.

    Article  CAS  Google Scholar 

  5. S. V. Saikova, T. V. Trofimova, A. Yu. Pavlikov, D. V. Karpov, D. I. Chistyakov, Yu. L. Mikhlin, Russ. Chem. Bull., 2020, 69, 1284; DOI: https://doi.org/10.1007/s11172-020-2899-z.

    Article  CAS  Google Scholar 

  6. M. I. Bruce, A. H. White, Austr. J. Chem., 1990, 43, 949; DOI: https://doi.org/10.1071/CH9900949.

    Article  CAS  Google Scholar 

  7. S. Jayanty, D. B. K. Kumar, T. P. Radhakrishnan, Synth. Met., 2000, 114, 37; DOI: https://doi.org/10.1016/S0379-6779(00)00204-6.

    Article  CAS  Google Scholar 

  8. I. E. Mikhailov, G. A. Dushenko, V. I. Minkin, Russ. J. Org. Chem., 2021, 57, 1757; DOI: https://doi.org/10.1134/S1070428021110014.

    Article  CAS  Google Scholar 

  9. C. D. Gheewala, B. E. Collins, T. H. Lambert, Science, 2016, 351, 961; DOI: https://doi.org/10.1126/science.aad0591.

    Article  CAS  Google Scholar 

  10. C. D. Gheewala, M. A. Radtke, J. Hui, A. B. Hon, T. H. Lambert, Org. Lett., 2017, 19, 4227; DOI: https://doi.org/10.1021/acs.orglett.7b01867.

    Article  CAS  Google Scholar 

  11. C. Müller, D. Vos, P. Jutzi, J. Organomet. Chem., 2000, 600, 127; DOI: https://doi.org/10.1016/S0022-328X(00)00060-7.

    Article  Google Scholar 

  12. G. J. Moxey, F. Ortu, L. G. Sidley, H. N. Strandberg, A. J. Blake, W. Lewis, D. L. Kays, Dalton Trans., 2014, 43, 4838; DOI: https://doi.org/10.1039/c3dt53234h.

    Article  CAS  Google Scholar 

  13. K. F. Kalz, A. Hausmann, S. Dechert, S. Meyer, M. John, F. Meyer, Chem. Eur. J., 2016, 22, 18190; DOI: https://doi.org/10.1002/chem.201603850.

    Article  CAS  Google Scholar 

  14. V. I. Minkin, I. E. Mikhailov, G. A. Dushenko, A. Zschunke, Russ. Chem. Rev., 2003, 72, 867; DOI: https://doi.org/10.1070/RC2003v072n10ABEH000848.

    Article  CAS  Google Scholar 

  15. I. D. Gridnev, M. K. C. Rosario, Organometallics, 2005, 24, 4519; DOI: https://doi.org/10.1021/om050039i.

    Article  CAS  Google Scholar 

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

    Article  CAS  Google Scholar 

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

    Article  CAS  Google Scholar 

  18. G. A. Dushenko, I. E. Mikhailov, O. I. Mikhailova, R. M. Minyaev, V. I. Minkin, Russ. Chem. Bull., 2015, 64, 2043; DOI: https://doi.org/10.1007/s11172-015-1115-z.

    Article  CAS  Google Scholar 

  19. I. E. Mikhailov, O. E. Kompan, G. A. Dushenko, V. I. Minkin, Mendeleev Commun., 1991, 1, 121; DOI: https://doi.org/10.1070/MC1991v001n04ABEH000074.

    Article  Google Scholar 

  20. G. A. Dushenko, I. E. Mikhailov, O. I. Mikhailova, R. M. Minyaev, V. I. Minkin, Russ. Chem. Bull., 2021, 70, 699; DOI: https://doi.org/10.1007/s11172-021-3139-x.

    Article  CAS  Google Scholar 

  21. M. I. Bruce, J. K. Walton, B. W. Skelton, A. H. White, J. Chem. Soc., Dalton Trans., 1983, 809; DOI: https://doi.org/10.1039/dt9830000809.

  22. C. H. Campbell, M. L. H. Green, J. Chem. Soc. A, 1971, 3282; DOI: https://doi.org/10.1039/j19710003282.

  23. H. Werner, H. Otto, Tri Ngo-Khac, Ch. Burschka, J. Organomet. Chem., 1984, 262, 123; DOI: https://doi.org/10.1016/S0022-328X(00)99128-9.

    Article  CAS  Google Scholar 

  24. H. Schumann, F. H. Goerlitz, A. Dietrich, Chem. Ber., 1989, 122, 1423; DOI: https://doi.org/10.1002/cber.19891220807.

    Article  CAS  Google Scholar 

  25. T. V. Baukova, Yu. L. Slovokhotov, Yu. T. Struchkov, J. Organomet. Chem., 1981, 220, 125; DOI: https://doi.org/10.1016/S0022-328X(00)83109-5.

    Article  CAS  Google Scholar 

  26. G. A. Dushenko, I. E. Mikhailov, O. E. Kompan, A. Zschunke, G. Reck, B. Schulz, C. Mugge, V. I. Minkin, Mendeleev Commun., 1997, 7, 127; DOI: https://doi.org/10.1070/MC1997v007n04ABEH000761.

    Article  Google Scholar 

  27. G. A. Dushenko, I. E. Mikhailov, A. Zschunke, G. Reck, B. Schulz, C. Mugge, V. I. Minkin, Mendeleev Commun., 1999, 9, 67; DOI: https://doi.org/10.1070/mc1999v009n02abeh001064.

    Article  Google Scholar 

  28. J. B. Foresman, E. Frisch, Exploring Chemistry with Electronic Structure Methods, Gaussian Inc., Pittsburg, 1996, 302 pp.

    Google Scholar 

  29. G. A. Dushenko, I. E. Mikhailov, G. Reck, B. Schulz, A. Zschunke, N. N. Kharabaev, V. I. Minkin, Russ. J. Org. Chem., 2002, 38, 982; DOI: https://doi.org/10.1023/A:1020897411534.

    Article  CAS  Google Scholar 

  30. G. A. Dushenko, I. E. Mikhailov, G. Reck, B. Schulz, A. Zschunke, V. I. Minkin, Russ. Chem. Bull., 2001, 50, 890; DOI: https://doi.org/10.1023/A:1011323629390.

    Article  CAS  Google Scholar 

  31. I. E. Mikhailov, G. A. Dushenko, G. Reck, B. Schulz, A. Zschunke, V. I. Minkin, Dokl. Chem., 2007, 412, 49; DOI: https://doi.org/10.1134/S0012500807020073.

    Article  CAS  Google Scholar 

Download references

Author information

Authors and Affiliations

  1. Institute of Physical and Organic Chemistry, Southern Federal University, 194/2 prosp. Stachki, 344090, Rostov-on-Don, Russian Federation

    G. A. Dushenko, I. E. Mikhailov, O. I. Mikhailova, R. M. Minyaev & 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. O. I. Mikhailova
    View author publications

    You can also search for this author in PubMed Google Scholar

  4. R. M. Minyaev
    View author publications

    You can also search for this author in PubMed Google Scholar

  5. 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

This work was financially supported by the Ministry of Science and Higher Education of the Russian Federation (State Assignment in the Field of Scientific Activity, Project No. 0852-2020-0019).

No human or animal subjects were used in this research.

The authors declare no competing interests.

Published in Russian in Izvestiya Akademii Nauk. Seriya Khimicheskaya, No. 9, pp. 1847–1855, September, 2022.

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., Mikhailova, O.I. et al. Structure elucidation of pentakis(methoxycarbonyl)- and amidinyltetrakis(methoxycarbonyl)cyclopentadienyl complexes of gold(I) by quantum chemistry methods. Russ Chem Bull 71, 1847–1855 (2022). https://doi.org/10.1007/s11172-022-3601-4

Download citation

  • Received:

  • Revised:

  • Accepted:

  • Published:

  • Issue Date:

  • DOI: https://doi.org/10.1007/s11172-022-3601-4

Key words

Search

Navigation