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Synthesis, X-ray characterization and catalytic homogenous alcohol oxidation activity of Co(II)–carboxamide complex with green oxidant (H2O2) under mild conditions

  • Hakan Ünver ORCID logo EMAIL logo

Abstract

In this study, a new air and moisture stable mononuclear cobalt(II)–carboxamide complex, [Co(TCrbx)2(CH3OH)2](ClO4)2, was synthesized and characterized (TCrbx = N-(4-methylpyridin-2-yl)thiophene-2-carboxamide). Complex characterization mainly was done with single crystal X-ray analysis. Ligand characterization was done with several spectroscopic techniques (Elemental Analysis, FT-IR, 1H NMR, 13C NMR). Cobalt(II) complex possesses distorted octahedral geometry coordinated with two carboxamide ligands at equatorial and two methanol ligands at axial positions and two perchlorate anions as counter ions. Synthesized complex was successfully tested as homogenous catalyst for the oxidation of benzyl alcohol with environmental friendly oxidant hydrogen peroxide (H2O2) under mild conditions. Benzaldehyde was selectively obtained with the conversion value of 99.5% in dimethyl formamide after 3-h reaction time at 50 °C with 133 TON value. Solvent and temperature effects were also investigated.


Corresponding author: Hakan Ünver, Department of Chemistry, Faculty of Science, Eskişehir Technical University, Eskişehir, 26210, Turkey, E-mail:

Acknowledgements

The author thankfully acknowledges the Medicinal Plants and Medicine Research Centre of Anadolu University, Eskişehir, Turkey for the use of X-ray Diffractometer and Eskişehir Technical University, Department of Chemistry, Eskişehir, Turkey for the other spectroscopic measurements.

  1. Author contribution: All the authors have accepted responsibility for the entire content of this submitted manuscript and approved submission.

  2. Research funding: None declared.

  3. Conflict of interest statement: The authors declare no conflict of interest, financial or otherwise.

References

1. Guo, Z., Liu, B., Zhang, Q., Deng, W., Wang, Y., Yang, Y. Recent advances in heterogeneous selective oxidation catalysis for sustainable chemistry. Chem. Soc. Rev. 2014, 43, 3480. https://doi.org/10.1039/c3cs60282f.Search in Google Scholar PubMed

2. Chen, B., Wang, L., Gao, S. Recent advances in aerobic oxidation of alcohols and amines to imines. ACS Catal. 2015, 5, 5851. https://doi.org/10.1021/acscatal.5b01479.Search in Google Scholar

3. Chepaikin, E. G., Bezruchenko, A. P., Menchikova, G. N., Gekhman, A. E. Homogeneous oxidation of alkanes: role of rhodium–alkyl complexes. J. Mol. Catal. A Chem. 2017, 426, 389. https://doi.org/10.1016/j.molcata.2016.07.026.Search in Google Scholar

4. Fu, R., Nielsen, R. J., Goddard, W. A. DFT virtual screening identifies rhodium–amidinate complexes as potential homogeneous catalysts for methane-to-methanol oxidation. ACS Catal. 2014, 4, 4455. https://doi.org/10.1021/cs5005322.Search in Google Scholar

5. Trach, Y. B., Makota, O. I., Bulgakova, L. V., Cherkasova, T. G., Nikol’skii, A. B., Varshavskii, Y. S. Binuclear rhodium organometallic complexes as catalysts of the liquid-phase 1-octene oxidation. Russ. J. Gen. Chem. 2010, 80, 1373. https://doi.org/10.1134/s1070363210070273.Search in Google Scholar

6. Qiao, C., Qui, D.-C., Lin, N., Zhu, J. W., Deng, W., Yao, Z. J. Half‐sandwich ruthenium‐based versatile catalyst for both alcohol oxidation and catalytic hydrogenation of carbonyl compounds in aqueous media. Appl. Organometal. Chem. 2019, 33, 4875. https://doi.org/10.1002/aoc.4875.Search in Google Scholar

7. Ramesh, M., Kumar, M. D., Jaccob, M., Therrien, B., Venkatachalam, G. Cyclometalated ruthenium(II) carbonyl complexes containing 2-(biphenylazo)phenolate ligands: synthesis, structure, DFT study and catalytic activity towards oxidation and transfer hydrogenation. Inorg. Chim. Acta 2018, 477, 40. https://doi.org/10.1016/j.ica.2018.02.023.Search in Google Scholar

8. Asensio, J. M., Sal, P. G., Andrés, R., Jesús, E. Synthesis of water-soluble palladium (II) complexes with N-heterocyclic carbene chelate ligands and their use in the aerobic oxidation of 1-phenylethanol. Dalton Trans. 2017, 46, 6785. https://doi.org/10.1039/c7dt00643h.Search in Google Scholar PubMed

9. Chai, H., Cao, Q., Dornan, L. M., Hughes, N. L., Brown, C. L., Nockemann, P., Li, J., Muldoon, M. J. Cationic palladium(II) complexes for catalytic Wacker‐type oxidation of styrenes to ketones using O2 as the sole oxidant. Eur. J. Inorg. Chem. 2017, 47, 5604. https://doi.org/10.1002/ejic.201700931.Search in Google Scholar

10. Liu, W., Sahoo, B., Junge, K., Beller, M. Cobalt complexes as an emerging class of catalysts for homogeneous hydrogenations. Acc. Chem. Res. 2018, 51, 1858. https://doi.org/10.1021/acs.accounts.8b00262.Search in Google Scholar PubMed

11. Ge, H., Chen, X., Yang, X. Hydrogenation of carbon dioxide to methanol catalyzed by iron, cobalt, and manganese cyclopentadienone complexes: mechanistic insights and computational design. Chem. Eur. J. 2017, 23, 8850. https://doi.org/10.1002/chem.201701200.Search in Google Scholar PubMed

12. Zhang, N., Wang, J., Huo, H., Chen, L., Shi, W., Li, C., Wang, J. Iron, cobalt and nickel complexes bearing hyperbranched iminopyridyl ligands: synthesis, characterization and evaluation as ethylene oligomerization catalysts. Inorg. Chim. Acta 2018, 469, 209. https://doi.org/10.1016/j.ica.2017.08.047.Search in Google Scholar

13. Li, C., Wang, F., Lin, Z., Zhang, N., Wang, J. Cobalt complexes based on hyperbranched salicylaldimine ligands as catalyst precursors for ethylene oligomerization. Appl. Organomet. Chem. 2017, 31, 3756. https://doi.org/10.1002/aoc.3756.Search in Google Scholar

14. Ansari, R. M., Kumar, L. M., Bhat, B. R., Air-stable cobalt(II) and nickel(II) complexes with Schiff base ligand for catalyzing Suzuki–Miyaura cross-coupling reaction. Russ. J. Coord. Chem. 2018, 44, 1. https://doi.org/10.1134/s1070328418010013.Search in Google Scholar

15. Li, C.-Y., Su, Y.-C., Lin, C.-H., Huang, H.-Y., Tsai, C.-Y., Lee, T.-Y., Ko, B.-T. Synthesis and characterization of trimetallic cobalt, zinc and nickel complexes containing amine-bis(benzotriazole phenolate) ligands: efficient catalysts for coupling of carbon dioxide with epoxides. Dalton Trans. 2017, 46, 15399. https://doi.org/10.1039/c7dt02841e.Search in Google Scholar PubMed

16. Tabrizi, L., Chiniforoshan, H., Mcardle, P. A cobalt(II) complex with anionic and neutral N-donor ligands: synthesis, crystal structure, and application as a heterogeneous catalyst for olefin epoxidation with tert-BuOOH. J. Coord. Chem. 2015, 68, 980. https://doi.org/10.1080/00958972.2015.1007964.Search in Google Scholar

17. Ramakrishna, D., Bhat, B. R., Hanumanthappa, S. K. T. Cobalt complex in a room temperature ionic liquid: a convenient recyclable reagent for catalytic epoxidation of cyclic alkenes. C. R. Chim. 2014, 17, 1071. https://doi.org/10.1016/j.crci.2013.12.004.Search in Google Scholar

18. Bhat, G. A., Rajendran, A., Murugavel, R. Polydentate 4‐pyridyl‐terpyridine containing discrete cobalt phosphonate and polymeric cobalt phosphate as catalysts for alcohol oxidation. Z. Anorg. Allg. Chem. 2018, 644, 692. https://doi.org/10.1002/zaac.201800091.Search in Google Scholar

19. Chakravorty, S., Das, B. K. Cobalt (II) 4-nitrobenzoates having pyridine as ancillary ligands and their catalytic role in the TBHP oxidation of alcohols. Polyhedron 2010, 29, 2006. https://doi.org/10.1016/j.poly.2010.03.014.Search in Google Scholar

20. Kopylovich, M. N., Mahmudov, K. T., Haukka, M., Figiel, P. J., Mizar, A., Silva, J. A. L., Pombeiro, A. J. L. Water‐soluble cobalt(II) and copper(II) complexes of 3‐(5‐chloro‐2‐hydroxy‐3‐sulfophenylhydrazo)pentane‐2,4‐dione as building blocks for 3D supramolecular networks and catalysts for TEMPO‐mediated aerobic oxidation of benzylic alcohols. Eur. J. Inorg. Chem. 2011, 4175. https://doi.org/10.1002/ejic.201100348.Search in Google Scholar

21. Myannik, K. A., Yarovenko, V. N., Beloglazkina, E. K., Moiseeva, A. A., Krayuskin, M. M. Novel copper(II), cobalt(II) and nickel(II) complexes with 5-(4-oxo-4H-chromen-3-yl)-4,5-dihydro-1,3,4-thiadiazole-2-carboxamide: synthesis, structure, spectroscopic studies. Polyhedron 2018, 139, 208. https://doi.org/10.1016/j.poly.2017.10.027.Search in Google Scholar

22. Meghdadi, S., Mirkhani, V., Mereiter, K. Electrochemical synthesis and crystal structure studies of defective dicubane tetranuclear hydroxo and carboxamide ligand bridged cobalt(II)–cobalt(III) complexes with carboxamides produced from unprotected hydroxyaromatic carboxylic acids. C. R. Chim. 2015, 18, 654. https://doi.org/10.1016/j.crci.2014.11.001.Search in Google Scholar

23. Patra, A. K., Ray, M., Murkherjee, R., Synthesis, J. crystal structure and properties of trigonal bipyramidal [M(L5)2(H2O)]·H2O complexes [M = cobalt(II) (S = 3/2) or copper(II) (S = 1/2); HL5 = N-(2-chloro-6-methylphenyl)pyridine-2-carboxamide]. Chem. Soc. Dalton Trans. 1999, 2461. https://doi.org/10.1039/a902851j.Search in Google Scholar

24. SMART, Bruker AXS, 2000.Search in Google Scholar

25. Dolomanov, O. V., Bourhis, L. J., Gildea, R. J., Howard, J. A. K., Puschmann, H. OLEX2: a complete structure solution, refinement and analysis program. J. Appl. Crystallogr. 2009, 42, 339. https://doi.org/10.1107/s0021889808042726.Search in Google Scholar

26. Sheldrick, G. M. SHELXT – Integrated space-group and crystal-structure determination. Acta Crystallogr. 2015, A71, 3. https://doi.org/10.1107/s2053273314026370.Search in Google Scholar PubMed PubMed Central

27. Sheldrick, G. M. Crystal structure refinement with SHELXL. Acta Crystallogr. 2015, C71, 3. https://doi.org/10.1107/s2053229614024218.Search in Google Scholar

28. Sheldrick, G. M. A short history of SHELX. Acta Crystallogr. 2008, A64, 112.10.1107/S0108767307043930Search in Google Scholar PubMed

29. Macrae, C. F., Edgington, P. R., McCabe, P., Pidcock, E., Shields, G. P., Taylor, R., Towler, M., Streek, J. Mercury: visualization and analysis of crystal structures. Appl. Crystallogr. 2006, 39, 453. https://doi.org/10.1107/s002188980600731x.Search in Google Scholar

30. Moon, S.-H., Kang, Y., Park, K.-M. Crystal structure of a CoII coordination polymer with a dipyridyl ligand: catena-poly[[bis(nitrato-κ2O,O′)cobalt(II)]-μ-N-(pyridin-2-ylmethyl)pyridine-3-amine-κ3N,N′:N′′]. Appl. Crystallogr. 2017, E73, 1696. https://doi.org/10.1107/s205698901701475x.Search in Google Scholar

31. Yang, L.-J., Song, W.-T., Luo, Y.-H., Sun, B.-W. Two complexes of copper(II) and cobalt(II) with N, O-chelating heterocyclic carboxylates: crystal structures, Hirshfeld surfaces, and thermal properties. Inorg. Nano-Metal Chem. 2017, 47, 493. https://doi.org/10.1080/15533174.2016.1186048.Search in Google Scholar

32. Moon, S.-H., Seo, J., Park, K.-M. Crystal structure of a zigzag CoII coordination polymer: catena-poly [[dichloridobis (methanol-κO) cobalt (II)]-μ-bis (pyridin-3-ylmethyl) sulfane-κ2N: N′]. Acta Crystallogr. 2017, E73, 1882. https://doi.org/10.1107/s2056989017016449.Search in Google Scholar

Supplementary Material

CCDC 1869717 contains the supplementary crystallographic data for complex.

The online version of this article offers supplementary material (https://doi.org/10.1515/zkri-2020-0038).

Received: 2020-04-03
Accepted: 2020-06-13
Published Online: 2020-07-01
Published in Print: 2020-07-28

© 2020 Walter de Gruyter GmbH, Berlin/Boston

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