Ruthenium(II) half-sandwich complexes containing N-substituted 5-nitrobenzimidazole: Synthesis, structures and catalytic transfer hydrogenation of ketones

Yıl 2019, Cilt:7 Sayı:2 (2019) (Özel Sayı), 63 - 72, 30.03.2019

Kenan Buldurun , İsmail Özdemir

https://doi.org/10.29130/dubited.473988

Cited By: 1

Öz

In this study,N-substituted 5-nitrobenzimidazole ligands
were reacted with [RuCl₂(p-cymene)]₂  and the corresponding complexes  were prepared and their structure were
elucidated by elemental analysis, IR and NMR spectroscopic techniques. The
synthesized Ru(II) complexes  were tested
as catalysts for the transfer hydrogenation (TH) of acetophenone to secondary
alcohols in the presence of KOH using 2–propanol as a hydrogen source at 82 ºC.
This complexes was found to be an active catalyst in the catalytic transfer
hydrogenation of ketones.

Anahtar Kelimeler

Benzimidazole, Catalysis, Ru(II) complexes, transfer hydrogenation

Kaynakça

• [1] M.S. Jana, A.K. Pramanik, S. Kundu, D. Sarkar, S. Jana, T.K. Mondal, ‘‘Ruthenium(I) complexes with NNS donor thioarylazoimidazole ligands with the cis-{Re(CO)2}+ core: Synthesis, characterization, electrochemical study and DFT calculation,’’ Inorg. Chim. Acta, 394, 583-590, 2013.
• [2] Z.K. Yu, F.L. Zeng, X.J. Sun, H.X. Deng, J.H. Dong, J.Z. Chen, H.M. Wang, C.X. Pei, ‘‘Two pseudo-N3 ligands and the catalytic activity of their ruthenium(II) complexes in transfer hydrogenation and hydrogenation of ketones,’’ J. Organomet. Chem., 692, 2306–2313, 2007.
• [3] S. Demir, F. Coşkun, İ. Özdemir, ‘‘The first used half sandwich ruthenium(II) complexes bearing benzimidazole moiety for N-alkylation of amines with alcohols,’’ J. Organomet. Chem., 755, 134-140, 2014.
• [4] İ. Özdemir, N. Şahin, B. Çetinkaya, ‘‘Transfer Hydrogenation of Ketones Catalyzed by 1-Alkylbenzimidazole Ruthenium(II) Complexes,’’ Monatsh. Chem., 138, 205-209, 2007.
• [5] R. Ramachandran, G. Prakash, M. Nirmala, P. Viswanathamurthi, J.G. Malecki, ‘‘Ruthenium (II) carbonyl complexes designed with arsine and PNO/PNS ligands as catalysts,’’ J. Organomet. Chem., 791, 130-140, 2015.
• [6] B. Çetinkaya,. B. Alıcı, İ. Özdemir, C. Bruneau, P.H. Dixneuf, ‘‘2-Imidazoline– and 1,4,5,6-tetrahydropyrimidine–ruthenium(II) complexes and catalytic synthesis of furan,’’ J. Organomet. Chem., 575, 187-192, 1999.
• [7] B. Çetinkaya, İ. Ozdemir, C. Bruneau, P.H. Dixneuf, ‘‘.Benzimidazole, Benzothiazole and Benzoxazole Ruthenium(II) Complexes; Catalytic Synthesis of 2,3-Dimethylfuran,’’ Eur. J. Inorg. Chem., 1,29-32, 2000.
• [8] K. Buldurun, N. Turan, A. Savcı, N. Çolak, ‘‘Synthesis, structural characterization and biological activities of metal(II) complexes withSchiff bases derived from 5-bromosalicylaldehyde: Ru(II) complexes transfer hydrogenation,’’ J. Saudi Chem. Soc., xxx-xxx, xxx(2018).
• [9] Y. Zhang, L. Liu, X. Cao, J. Zhao, ‘‘Synthesis, single crystal structure and efficient catalysis for alcohol oxidation of a novel Ru(II) complex with both a N,N,N-tridentate ligand and a pyridinedicarboxylate,’’ Polyhedron, 105, 170–177, 2016.
• [10] J.M. Gichumbi, H.B. Friedrich, ‘‘Half-sandwich complexes of platinum group metals (Ir, Rh, Ru and Os) and some recent biological and catalytic applications,’’ J. Organomet. Chem., 866, 123-143, 2018.
• [11] K. Buldurun, “Benzimidazol Çekirdeği İçeren Azol Komplekslerinin Sentezi ve Katalitik Özellikleri,” Doktora tezi, Kimya Bölümü, İnönü Üniversitesi, Malatya, Türkiye, 2015.
• [12] K.S. Singh, W. Kaminsky, ‘‘Arene ruthenium(II) azido complexes incorporating N⋂O chelate ligands: Synthesis, spectral studies and 1,3-dipolar-cycloaddition to a coordinated azide in ruthenium(II) compounds,’’ Polyhedron, 68, 279–286, 2014.
• [13] N. Turan, K. Buldurun, ‘‘Synthesis, characterization and antioxidant activity of Schiff base and its metalcomplexes with Fe(II), Mn(II), Zn(II), and Ru(II) ions: Catalytic activity of ruthenium(II) complex,’’ Eur. J. Chem., 9, 22‐29, 2018.
• [14] W.-G.Jia, H. Zhang, T. Zhang, S. Ling, ‘‘Synthesis, structure and catalytic activities of half-sandwich ruthenium complexes based on Schiff Base ligands,’’ Inorg. Chem. Commun., 66, 15–18, 2016.
• [15] L. Wang, Q. Yang, H. Chen, R. X. Li, ‘‘A novel cationic dinuclear ruthenium complex: Synthesis, characterizasyon and catalytic activity in the transfer hydrogenation of ketons,’’ Inorg. Chim. Acta,, 14, 1884-1888, 2011.
• [16] G. Zassinovich, G. Mestroni, S. Gladiali, ‘‘ Asymmetric hydrogen transfer reactions promoted by homogeneous transition metal catalysts,’’ Chem. Rev., 92, 1051-1059, 1992.
• [17] S.A. Moya, C.N. Vergara, K. Brown, V. Artigas, M. Fuentealba, V. Guerchais, ‘‘ Transfer hydrogenation of N-benzlideneaniline catalzed by ruthenium complexes with pincer-type phosphorous nitrogen ligands using propan-2-ol as the hydrogen source,’’ Catal. Commun., 99, 150-153, 2018.
• [18] T. S. Manikandan, S. Saranya, R. Ramesh, ‘‘ Synthesis and catalytic evaluation of rutheniun(II) benzhydrazone complex in transfer hydrogenation of ketones,’’ Tetrahedron Lett., 57, 3764-3769, 2016.
• [19] D. Pandiarajan, R. Ramesh, ‘‘Ruthenium(II) half-sandwich complexes containing thioamides: Synthesis, structures and catalytic transfer hydrogenation of ketones,’’ J. Organomet. Chem., 723, 26-35, 2013.
• [20] D. Mercan, E. Çetinkaya, E. Şahin, ‘‘Ru(II) arene complexes with N-substitued 3,4-dihydroquinazoline ligands and ctalytic activity for transfer hydrojenation reaction,’’ Inorg. Chim. Acta, 400, 74-81, 2013.
• [21] D.D. Perrin, W.F.F. Armarego, D.R. Perrin, ‘‘Purification of laboratory chemicals, Pergamon,’’ Press Ltd, Sec. Ed., 1980.
• [22] M.A. Bennett, T.N. Huang, T.W. Matheson, A.K. Smith, ‘‘ (η6-Hexamethylbenzene)Ruthenium Complexes,’’ Inorganic Synth., 21, 74-78, 1982.