Skip to main content
SpringerLink
Log in

New Polymorph of 1,3-Bis(2,6-di-isopropylphenyl)-4,5-Dichloroimidazole-2-Ylidene and a Cobalt Complex with this Compound

  • Published:
Journal of Structural Chemistry Aims and scope Submit manuscript

Abstract

A new crystal modification of the N-heterocyclic carbene 1,3-bis(2,6-di-isopropylphenyl)-4,5-dichloroimidazol-2-ylidene (IPrCl, 1) is obtained and structurally characterized. The hydrolysis of this compound leads to the formation of the (IPrClH)+Cl– (2) hydrochloride. The [Co3(Piv)4Cl2(IPrCl)2]·2C7H8 (3·2C7H8) mixed-ligand complex is synthesized by the interaction of the [Co(Piv)2]n cobalt pivalate with IPrCl and is characterized by XRD.

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
Scheme 1
Fig. 2

REFERENCES

  1. N-Heterocyclic Carbenes: From Laboratory Curiosities to Efficient Synthetic Tools / Ed. S. Díez-González. Cambridge: RSC Publishing, 2017.

  2. M. N. Hopkinson, C. Richter, M. Schedler, and F. Glorius. An overview of N-heterocyclic carbenes. Nature, 2014, 510, 485-496. https://doi.org/10.1038/nature13384

    Article  ADS  CAS  PubMed  Google Scholar 

  3. V. M. Chernyshev, O. V. Khazipov, M. A. Shevchenko, D. V. Pasyukov, J. V. Burykina, M. E. Minyaev, D. B. Eremin, and V. P. Ananikov. Discovery of the N–NHC coupling process under the conditions of Pd/NHC- and Ni/NHC-catalyzed Buchwald–Hartwig amination. Organometallics, 2022, 41, 1519-1531. https://doi.org/10.1021/acs.organomet.2c00166

    Article  CAS  Google Scholar 

  4. A. Yu. Chernenko, A. V. Astakhov, V. V. Kutyrev, E. G. Gordeev, J. V. Burykina, M. E. Minyaev, V. N. Khrustalev, V. M. Chernyshev, and V. P. Ananikov. Stabilization of the Pd–NHC framework with 1,2,4-triazol-5-ylidene ligands toward decomposition in alkaline media. Inorg. Chem. Front., 2021, 8, 3382-3401. https://doi.org/10.1039/D1QI00453K

    Article  CAS  Google Scholar 

  5. E. V. Ilyakina, A. I. Poddel′sky, A. V. Piskunov, G. K. Fukin, A. S. Bogomyakov, V. K. Cherkasov, and G. A. Abakumov. The interaction of N,N′-bis(2,6-dimethylphenyl)imidazol-2-ylidene with o-benzosemiquinonato zinc(II) and indium(III) complexes. New J. Chem., 2012, 36, 1944-1948. https://doi.org/10.1039/C2NJ40490G

    Article  CAS  Google Scholar 

  6. I. N. Meshcheryakova, K. V. Arsenyeva, G. K. Fukin, V. K. Cherkasov, and A. V. Piskunov. Stable N-heterocyclic carbene derivatives of copper(I) and silver(I) containing radical anion redox active ligands. Mendeleev Commun., 2020, 30, 592-595. https://doi.org/10.1016/j.mencom.2020.09.013

    Article  CAS  Google Scholar 

  7. E. V. Bellan, A. I. Poddel'sky, N. A. Protasenko, A. S. Bogomyakov, G. K. Fukin, V. K. Cherkasov, and G. A. Abakumov. Bis-o-benzosemiquinonato cobalt(II) and nickel(II) complexes with neutral N-heterocyclic carbene ligand: Synthesis, structure and magnetic properties. ChemistrySelect, 2016, 1, 2988-2992. https://doi.org/10.1002/slct.201600506

    Article  CAS  Google Scholar 

  8. D. V. Pasyukov, M. A. Shevchenko, A. V. Astakhov, M. E. Minyaev, Y. Zhang, V. M. Chernyshev, and V. P. Ananikov. New class of RSO2–NHC ligands and Pd/RSO2–NHC complexes with tailored electronic properties and high performance in catalytic C–C and C–N bonds formation. Dalton Trans., 2023, 52, 12067-12086. https://doi.org/10.1039/D3DT02296J

    Article  CAS  PubMed  Google Scholar 

  9. K. E. Shepelenko, K. A. Nikolaeva, M. A. Shevchenko, Yu. N. Tkachenko, M. E. Minyaev, and V. M. Chernyshev. Ruthenium complexes with chelating carboxylate-NHC ligands as efficient catalysts for C–H arylation in water. Mendeleev Commun., 2022, 32, 205-207. https://doi.org/10.1016/j.mencom.2022.03.017

    Article  CAS  Google Scholar 

  10. A. V. Astakhov, O. V. Khazipov, A. Yu. Chernenko, D. V. Pasyukov, A. S. Kashin, E. G. Gordeev, V. N. Khrustalev, V. M. Chernyshev, and V. P. Ananikov. A new mode of operation of Pd–NHC systems studied in a catalytic Mizoroki–Heck reaction. Organometallics, 2017, 36, 1981-1992. https://doi.org/10.1021/acs.organomet.7b00184

    Article  CAS  Google Scholar 

  11. D. V. Pasyukov, M. A. Shevchenko, K. E. Shepelenko, O. V. Khazipov, Ju. V. Burykina, E. G. Gordeev, M. E. Minyaev, V. M. Chernyshev, and V. P. Ananikov. One-step access to heteroatom-functionalized imidazol(in)ium salts. Angew. Chem., Int. Ed., 2022, 61, e202116131. https://doi.org/10.1002/anie.202116131

    Article  Google Scholar 

  12. K. L. Fillman, J. A. Przyojski, M. H. Al-Afyouni, Z. J. Tonzetich, and M. L. Neidig. A combined magnetic circular dichroism and density functional theory approach for the elucidation of electronic structure and bonding in three- and four-coordinate iron(II)–N-heterocyclic carbene complexes. Chem. Sci., 2015, 6, 1178-1188. https://doi.org/10.1039/C4SC02791D

    Article  CAS  PubMed  Google Scholar 

  13. T. Tsushima, H. Tanaka, K. Nakanishi, M. Nakamoto, and H. Yoshida. Origins of internal regioselectivity in copper-catalyzed borylation of terminal alkynes. ACS Catal., 2021, 11, 14381-14387. https://doi.org/10.1021/acscatal.1c04244

    Article  CAS  Google Scholar 

  14. A. J. Arduengo, F. Davidson, H. V. R. Dias, J. R. Goerlich, D. Khasnis, W. J. Marshall, and T. K. Prakasha. An air stable carbene and mixed carbene “dimmers”. J. Am. Chem. Soc., 1997, 119, 12742-12749. https://doi.org/10.1021/ja973241o

    Article  CAS  Google Scholar 

  15. M. L. Cole, C. Jones, and P. C. Junk. Studies of the reactivity of N-heterocyclic carbenes with halogen and halide sources. New J. Chem., 2002, 26, 1296-1303. https://doi.org/10.1039/B204422F

    Article  CAS  Google Scholar 

  16. S. K. Furfari, M. R. Gyton, D. Twycross, and M. L. Cole. Air stable NHCs: A study of stereoelectronics and metallorganic catalytic activity. Chem. Commun., 2015, 51, 74-76. https://doi.org/10.1039/C4CC06809B

    Article  CAS  Google Scholar 

  17. T. Simler, A. A. Danopoulos, and P. Braunstein. N-heterocyclic carbene complexes of cobalt. In: Comprehensive Organometallic Chemistry IV / Eds. G. Parkin, K. Meyer, D. O′Hare. Amsterdam: Elsevier, 2022, Ch. 7.11. https://doi.org/10.1016/B978-0-12-820206-7.00109-8

    Chapter  Google Scholar 

  18. C. F. Harris, M. B. Bayless, N. P. van Leest, Q. J. Bruch, B. N. Livesay, J. Bacsa, K. I. Hardcastle, M. P. Shores, B. de Bruin, and J. D. Soper. Redox-active bis(phenolate) N-heterocyclic carbene [OCO] pincer ligands support cobalt electron transfer series spanning four oxidation states. Inorg. Chem., 2017, 56, 12421-12435. https://doi.org/10.1021/acs.inorgchem.7b01906

    Article  CAS  PubMed  Google Scholar 

  19. K. Tokmic, C. R. Markus, L. Zhu, and A. R. Fout. Well-defined cobalt(I) dihydrogen catalyst: Experimental evidence for a Co(I)/Co(III) redox process in olefin hydrogenation. J. Am. Chem. Soc., 2016, 138, 11907-11913. https://doi.org/10.1021/jacs.6b07066

    Article  CAS  PubMed  Google Scholar 

  20. D. Wang, Y. Lai, P. Wang, X. Leng, J. Xiao, and L. Deng. Markovnikov hydrosilylation of alkynes with tertiary silanes catalyzed by dinuclear cobalt carbonyl complexes with NHC ligation. J. Am. Chem. Soc., 2021, 143, 12847-12856. https://doi.org/10.1021/jacs.1c06583

    Article  CAS  PubMed  Google Scholar 

  21. X.-N. Yao, J.-Z. Du, Y.-Q. Zhang, X.-B. Leng, M.-W. Yang, S.-D. Jiang, Z.-X. Wang, Z.-W. Ouyang, L. Deng, B.-W. Wang, and S. Gao. Two-coordinate Co(II) imido complexes as outstanding single-molecule magnets. J. Am. Chem. Soc., 2017, 139, 373-380. https://doi.org/10.1021/jacs.6b11043

    Article  CAS  PubMed  Google Scholar 

  22. S. A. Nikolaevskii, P. A. Petrov, T. S. Sukhikh, D. S. Yambulatov, M. A. Kiskin, M. N. Sokolov, and I. L. Eremenko. Simple synthetic protocol to obtain 3d-4f-heterometallic carboxylate complexes of N-heterocyclic carbenes. Inorg. Chim. Acta, 2020, 508, 119643. https://doi.org/10.1016/j.ica.2020.119643

    Article  CAS  Google Scholar 

  23. D. S. Yambulatov, P. A. Petrov, Yu. V. Nelyubina, A. A. Starikova, A. A. Pavlov, D. Yu. Aleshin, S. A. Nikolaevskii, M. A. Kiskin, M. N. Sokolov, and I. L. Eremenko. Rare example of structurally characterized mononuclear N-heterocyclic carbene containing zinc carboxylate. Mendeleev Commun., 2020, 30, 293-295. https://doi.org/10.1016/j.mencom.2020.05.010

    Article  CAS  Google Scholar 

  24. D. S. Yambulatov, S. A. Nikolaevskii, M. A. Shmelev, K. A. Babeshkin, D. V. Korchagin, N. N. Efimov, A. S. Goloveshkin, P. A. Petrov, M. A. Kiskin, M. N. Sokolov, and I. L. Eremenko. Heterometallic CoII–LiI carboxylate complexes with N-heterocyclic carbene, triphenylphosphine and pyridine: A comparative study of magnetic properties. Mendeleev Commun., 2021, 31, 624-627. https://doi.org/10.1016/j.mencom.2021.09.011

    Article  CAS  Google Scholar 

  25. P. A. Petrov, S. A. Nikolaevskii, D. S. Yambulatov, T. S. Sukhikh, A. A. Starikova, M. A. Kiskin, M. N. Sokolov, and I. L. Eremenko. Heteroleptic cobalt complexes with abnormally coordinated N-heterocyclic carbene. Russ. J. Coord. Chem., 2023, 49, 407-413. https://doi.org/10.1134/S1070328423600274

    Article  CAS  Google Scholar 

  26. P. A. Petrov, S. A. Nikolaevskii, D. S. Yambulatov, T. S. Sukhikh, A. A. Starikova, M. A. Kiskin, M. N. Sokolov, and I. L. Eremenko. Heteroleptic anionic cobalt(II) pivalate complex with a bridging trimethylsiloxy ligand: Synthesis, structure, and formation mechanism. Russ. J. Inorg. Chem., 2023, 68, 1228-1236. https://doi.org/10.1134/S0036023623601460

    Article  CAS  Google Scholar 

  27. The Chemist′s Companion: A Handbook of Practical Data, Techniques, and References / Eds. A. Gordon and R. Ford. New York: Wiley, 1972.

  28. M. A. Golubnichaya, A. A. Sidorov, I. G. Fomina, M. O. Ponina, S. M. Deomidov, S. E. Nefedov, I. L. Eremenko, and I. I. Moiseev. New polynuclear cobalt trimethylacetate complexes: Synthesis and structure. Russ. Chem. Bull., 1999, 48, 1751-1756. https://doi.org/10.1007/BF02494824

    Article  CAS  Google Scholar 

  29. I. G. Fomina, G. G. Aleksandrov, Zh. V. Dobrokhotova, O. Yu. Proshenkina, M. A. Kiskin, Yu. A. Velikodnyi, V. N. Ikorskii, V. M. Novotortsev, and I. L. Eremenko. High-spin carboxylate polymers [M(OOCCMe3)2]n of group VIII 3d metals. Russ. Chem. Bull., 2006, 55, 1909-1919. https://doi.org/10.1007/s11172-006-0532-4

    Article  CAS  Google Scholar 

  30. A. J. Arduengo III, R. Krafczyk, R. Schmutzler, H. A. Craig, J. R. Goerlich, W. J. Marshall, and M. Unverzagt. Imidazolylidenes, imidazolinylidenes and imidazolidines. Tetrahedron, 1999, 55, 14523-14534. https://doi.org/10.1016/S0040-4020(99)00927-8

    Article  CAS  Google Scholar 

  31. P. A. Petrov, A. I. Smolentsev, A. S. Bogomyakov, and S. N. Konchenko. Novel vanadium complexes supported by a bulky tris(pyrazolyl)borate ligand. Polyhedron, 2017, 129, 60-64. https://doi.org/10.1016/j.poly.2017.03.033

    Article  CAS  Google Scholar 

  32. Apex3 software suite: Apex3, SADABS-2016/2 and SAINT, version 2018.7-2. Madison, WI, USA: Bruker AXS, 2017.

  33. G. M. Sheldrick. SHELXT - Integrated space-group and crystal-structure determination. Acta Crystallogr., Sect. A: Found. Adv., 2015, 71(1), 3-8. https://doi.org/10.1107/s2053273314026370

    Article  ADS  Google Scholar 

  34. G. M. Sheldrick. Crystal structure refinement with SHELXL. Acta Crystallogr., Sect. C: Struct. Chem., 2015, 71(1), 3-8. https://doi.org/10.1107/s2053229614024218

    Article  ADS  Google Scholar 

  35. O. V. Dolomanov, L. J. Bourhis, R. J. Gildea, J. A. K. Howard, and H. Puschmann. OLEX2: A complete structure solution, refinement and analysis program. J. Appl. Crystallogr., 2009, 42, 339-341. https://doi.org/10.1107/S0021889808042726

    Article  CAS  Google Scholar 

  36. M. K. Denk, J. M. Rodezno, S. Gupta, and A. J. Lough. Synthesis and reactivity of subvalent compounds: Part 11. Oxidation, hydrogenation and hydrolysis of stable diamino carbenes. J. Organomet. Chem., 2001, 617/618, 242-253. https://doi.org/10.1016/S0022-328X(00)00551-9

    Article  CAS  Google Scholar 

  37. T. L. Amyes, S. T. Diver, J. P. Richard, F. M. Rivas, and K. Toth. Formation and stability of N-heterocyclic carbenes in water: The carbon acid pKa of imidazolium cations in aqueous solution. J. Am. Chem. Soc., 2004, 126, 4366-4374. https://doi.org/10.1021/ja039890j

    Article  CAS  PubMed  Google Scholar 

  38. O. Holloczki, P. Terleczky, D. Szieberth, G. Mourgas, D. Gudat, and L. Nyulaszi. Hydrolysis of imidazole-2-ylidenes. J. Am. Chem. Soc., 2011, 133, 780-789. https://doi.org/10.1021/ja103578y

    Article  CAS  PubMed  Google Scholar 

  39. A. V. Astakhov, O. V. Khazipov, E. S. Degtyareva, V. N. Khrustalev, V. M. Chernyshev, and V. P. Ananikov. Facile hydrolysis of nickel(II) complexes with N-heterocyclic carbene ligands. Organometallics, 2015, 34, 5759-5766. https://doi.org/10.1021/acs.organomet.5b00856

    Article  CAS  Google Scholar 

  40. V. M. Chernyshev, O. V. Khazipov, M. A. Shevchenko, A. Yu. Chernenko, A. V. Astakhov, D. B. Eremin, D. V. Pasyukov, A. S. Kashin, and V. P. Ananikov. Revealing the unusual role of bases in activation/deactivation of catalytic systems: O–NHC coupling in M/NHC catalysis. Chem. Sci., 2018, 9, 5564-5577. https://doi.org/10.1039/C8SC01353E

    Article  CAS  PubMed  PubMed Central  Google Scholar 

Download references

Funding

This work was funded by the Russian Science Foundation (project No. 19-13-00436-P).

Author information

Authors and Affiliations

  1. Nikolaev Institute of Inorganic Chemistry, Siberian Branch, Russian Academy of Sciences, Novosibirsk, Russia

    P. A. Petrov, E. A. Filippova, N. B. Kompankov, T. S. Sukhikh & M. N. Sokolov

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

    S. A. Nikolaevskii, M. A. Kiskin & I. L. Eremenko

Authors
  1. P. A. Petrov
    View author publications

    You can also search for this author in PubMed Google Scholar

  2. S. A. Nikolaevskii
    View author publications

    You can also search for this author in PubMed Google Scholar

  3. E. A. Filippova
    View author publications

    You can also search for this author in PubMed Google Scholar

  4. N. B. Kompankov
    View author publications

    You can also search for this author in PubMed Google Scholar

  5. T. S. Sukhikh
    View author publications

    You can also search for this author in PubMed Google Scholar

  6. M. A. Kiskin
    View author publications

    You can also search for this author in PubMed Google Scholar

  7. M. N. Sokolov
    View author publications

    You can also search for this author in PubMed Google Scholar

  8. I. L. Eremenko
    View author publications

    You can also search for this author in PubMed Google Scholar

Corresponding authors

Correspondence to P. A. Petrov or S. A. Nikolaevskii.

Ethics declarations

The authors of this work declare that they have no conflicts of interest.

Additional information

Russian Text © The Author(s), 2024, published in Zhurnal Strukturnoi Khimii, 2024, Vol. 65, No. 1, 120712.https://doi.org/10.26902/JSC_id120712

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

Supplementary material

Rights and permissions

Reprints and permissions

About this article

Check for updates. Verify currency and authenticity via CrossMark

Cite this article

Petrov, P.A., Nikolaevskii, S.A., Filippova, E.A. et al. New Polymorph of 1,3-Bis(2,6-di-isopropylphenyl)-4,5-Dichloroimidazole-2-Ylidene and a Cobalt Complex with this Compound. J Struct Chem 65, 117–124 (2024). https://doi.org/10.1134/S0022476624010116

Download citation

  • Received:

  • Revised:

  • Accepted:

  • Published:

  • Issue Date:

  • DOI: https://doi.org/10.1134/S0022476624010116

Keywords

Search

Navigation