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

Öz 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).

Anahtar Kelimeler:

Transfer hydrogenation, Ruthenium, Catalysis, Ketone

PDF

___

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.