Catalytic activity of two Ru(II) complexes in transfer hydrogenation reaction of simple ketones

Year 2020, Volume: 9 Issue: 1, 9 - 16, 10.06.2020

Nevin Arslan

Abstract

Hydrogen transfer reduction reactions have been attracted significant attention in organic synthesis due to their operational easiness. For this purpose, two Ru(II) complexes of P-N-P ligand were prepared starting from [Ru(η6-p-cymene) (μ-Cl)Cl]2. Then, their catalytic activity was investigated in the transfer hydrogenation of different simple alkyl and aryl alkyl ketones to respective alcohols in the existence of isopropanol as the hydrogen source. Notably, 2 exhibits a good catalytic activity and affords the respective alcohols with good conversions up to 98 % (TOF: 392 h-1).

Keywords

Transfer hydrogenation , Ruthenium , Catalysis , Ketone

References

• J. G. de Vries., C, J. Elsevier, The Handbook of Homogeneous Hydrogenation, Wiley-VCH, 2006.
• W. Niklas, K. Jürgen, Transfer Hydrogenation of Carbon Dioxide to Methanol Using a Molecular Ruthenium-Phosphine Catalyst, Chem. Cat. Chem, 11 (2019) 1-6.
• N. H. Anh, H. Loi, Structure–activity relationship study of halfsandwich metal complexes in aqueous transfer hydrogenation catalysis, Inorg. Chem. Front. 7 (2020) 583-591.
• F. A. Georgy, van P. Robbert, J. M. H Emiel, P.A. Evgeny, Catalytic (de)hydrogenation promoted by non-precious metals – Co, Fe and Mn: recent advances in an emerging field, Chem. Soc. Rev. 47 (2018) 1459-1483.
• M. Aydemir, A. Baysal, S. Özkar, L. Tatar, trans- and cis-Ru(II) aminophosphine complexes: Syntheses, X-ray structures and catalytic activity in transfer hydrogenation of acetophenone derivatives, Inorg. Chem. Acta. 367 (2011) 166-172.
• M. Aydemir, A. Baysal, N. Gurbuz, İ. Ozdemir, B. Gumgum, S. Ozkar, L.T. Yıldırım, Appl. Organomet. Chem. 24 (2010) 17-24.
• M-M. Felicite, P. Lo¨nnecke, EV. Novikova, GP. Belov, H-H. Evamarie, Oligodentate P,N ligands: N,N,N′,N′-tetrakis(diphenylphosphanyl)-1,3-diaminobenzene complexes of rhodium, nickel and palladium, Dalton Trans. (2005) 3326–3330.
• M. Aydemir, A. Baysal, S. Özkar, L. Tatar, Ruthenium complexes of aminophosphine ligands and their use as pre-catalysts in the transfer hydrogenation of aromatic ketones: X-ray crystal structure of thiophene-2-(N-diphenylthiophosphino)methylamine, Polyhedron 30(5) (2011) 796-804.
• M.A. Bennet, A.K. Smith, Arene ruthenium (II) complexes formed by dehydrogenation of cyclohexadienes with ruthenium (III) trichloride, Chem. Soc. Dalton. Trans. (1974) 233-241.
• A. Baysal, M. Aydemir, F. Durap, B. Gümgüm, S. Özkar, L.T. Yıldırım, Synthesis and characterizations of 3,3'-Bis(diphenylphosphinoamine)-2,2'-bipyridine and 3,3'-Bis(diphenylphosphinite)-2,2'-bipyridine and their chalcogenides, Polyhedron, 26 (2007) 3373-3378.
• M. Aydemir, A. Baysal, F. Durap, B. Gümgüm, S. Özkar, L.T. Yıldırım, Synthesis and characterization of new transition metal complexes of thiophene-2-methylamine: X-ray crystal structure of palladium (II), platinum (II) complexes and use of palladium(II) complexes as pre-catalyst in Heck and Suzuki cross-coupling reaction, Appl. Organomet. Chem, 23 (2009) 467-475.
• A.D. Burrows, M.F. Mahona, M. T. Palmera, Ether functionalised aminophosphines: synthesis and coordination chemistry of palladium(II) and platinum(II) complexes, J. Chem. Soc. Dalton Trans. (2000) 1669-1677.
• M.S. Balakrishna, R. Panda, D.C. Smith Jr, A. Klaman, S.P. Nolan, Ruthenium(II) Chemistry of Phosphorus Based Ligands. Ph2PN(R)PPh2 (R=Me or Ph) and Ph2PN(Ph)P(E)Ph2 (E = S or Se). Solution Thermochemical study of Ligand Substitution Reactions in the Cp'RuCl(COD) (Cp' = Cp, Cp*; COD = cyclooctadiene) System, J. Organometal.Chem, 599 (2000) 159-165.
• M.S. Balakrishna, K. Ramaswarmy, R.M. Abhyankar, Transition Metal Chemistry of Phosphorus based ligands. Ruthenium (II) Chemistry of Bis(diphosphino)amines, X2PN(R)PX2 (R=H or Ph, X=Ph; R=Ph, X2=O2C6H4), J. Organometal Chem. 560 (1998) 131-136.
• J. W. Faller, A. R. Lavoie, Catalysts for the Asymmetric Transfer Hydrogenation of Ketones Derived from l-Prolinamide and (p-CymeneRuCl2)2 or (Cp*RhCl2)2, Organometallics 20 (2001) 5245-5247.
• J.-X. Gao, X.-D. Yi, P.-P. Xu, C. -L. Tang, H.-L. Wan, T. Ikariya, New chiral cationic rhodium–aminophosphine complexes for asymmetric transfer hydrogenation of aromatic ketones, J. Organometal. Chem. 592 (1999) 290-295.
• M. Aydemir, A. Baysal, Ruthenium-catalyzed transfer hydrogenation of aromatic ketones with aminophosphine or bis(phosphino)amine ligands derived from isopropyl substituted anilines, Polyhedron 29 (2010) 1219-1224.
• Y. Chen, S. Yekta, A.K. Yudin, Modified BINOL Ligands in Asymmetric Catalysis, Chem. Rev. 103 (2003) 3155-3212.
• T. Jerphagnon, J.L. Renaud, C. Bruneau, Chiral monodentate phosphorus ligands for rhodium-catalyzed asymmetric hydrogenation, Tetrahedron: Asymmetry, 15 (2004) 2101-2111.