Nermin MERİÇ, Cezmi KAYAN, Murat AYDEMİR, Yusuf Selim OCAK, Akın BAYSAL, Hamdi TEMEL

İki çekirdekli rutenyum II aren komplekslerinin ketonların transfer hidrojenasyonuna uygulanması

Geçifl metal katalizörlerinin transfer hidrojenasyon reaksiyonuyla organik substratlara hidrojen katılmasıveya çıkarılması önemli bir sentetik araçtır. Bu amaçla, N3,N3'-di-2-hidroksibenziliden-[2,2']bipiridinil3,3'-diamin bilefliğinden elde edilen bir P-O ligandı olan N3,N3'-di-2- difenilfosfino benziliden-[2,2']bipiridinil3,3'-diaminin bir dizi metal kompleksi sentezlendi. N3,N3'-di-2- difenilfosfino benziliden-[2,2']bipiridinil3,3'-diaminin [Ru η-benzen µ-Cl Cl] yada [Ru η-p-simen µ-Cl Cl]2 ile reaksiyonu köprülü ve ikiçekirdekli [CH16N4{OPPh2-Ru η6-benzen Cl2}2] 1 ve [Ckomplekslerini vermektedir. Ru II -bisfosfinit kompleksleri ayrıca basit birçok alkil ve aril alkil ketonuntransfer hidrojenasyonunda katalizör olarak kullanıldı ve iyi düzeyde % 99'a kadar dönüflümler eldeedildi

Application of dinuclear ruthenium II arene complexes in transfer hydrogenation of ketones

The ability of transition metal catalysts to add or remove hydrogen from organic substrates by transferhydrogenation process is a valuable synthetic tool. For this aim, a series of metal complexes with a P-Oligand, N3,N3'-di-2- diphenylphosphino benzylidene-[2,2']bipyridinyl-3,3'-diamine derived from N3,N3'di-2-hydroxybenzylidene-[2,2']bipyridinyl-3,3'-diamine were synthesized. Reaction of N3,N3'-di-2 diphenylphosphino benzylidene-[2,2']bipyridinyl-3,3'-diamine with [Ru η6-benzene µ-Cl Cl]2 or [Ru η6p-cymene µ-Cl Cl]2 gave bridged dinuclear complexes [C24H16N4{OPPh2-Ru η6-benzene Cl2}2] 1 and[C24H16N4{OPPh2-Ru η6-p-cymene Cl}2] 2, respectively. Ru II -bisphosphinite complexes have also beenused as catalysts for the transfer hydrogenation of a variety of simple alkyl and aryl alkyl ketones and goodconversions up to 99 % were obtained

Keywords:

Bis phosphinite, Transfer hydrogenation, Ruthenium, Catalysis, Ketone,

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1. S. Gladiali, E. Alberico, in Transition Metals for Organic Synthesis, ed. M. Beller and C. Bolm, WileyVCH, Weinheim, 2004, vol. 2, pp. 145.

2. S. E. Clapham, A. Hadzovic, R. H. Morris, Coord. Chem. Rev. 248 (2004) 2201-2237.

3. J. E. Backvall, J. Organomet. Chem. 652 (2002) 105- 111.

4. J. S. M. Samec, Jan-E. Backvall, P. G. Andersson, P. Brandt, Chem. Soc. Rev. 35 (2006) 237-248.

5. J. S. M. Samec, Jan-E. Backvall, Chem. Eur. J. 8 (2002) 2955-2961.

6. (a) D. A. Alonso, S. J. M. Nordin; P. Roth, T. Tarnai, P. G. Andersson, J. Org. Chem. 65 (2000) 3116-3122. (b) D. Totev, A. Salzer, D. Carmona, L. A. Oro, F. J. Lahoz, I. T. Dobrinovitch, Inorg. Chim. Acta 357 (2004) 2889-2898.

7. R. V. Wisman, J. G. de Vries, B.-J. Deelman, H. J. Heeres, Organic Process Res. & Develop. 10 (2006) 423-429.

8. J. Bayardon, D. Sinou, O. Holczknecht, L. Mercs, G. Pozzi, Tetrahedron: Asymmetry 16 (2005) 2319- 2327.

9. (a) K. Everaere, A. Mortreux, J.-F. Carpentier, Adv. Synth. Catal. 345 (2003) 67-77; (b) K. Aboulaala, C. Goux-Henry, D. Sinou, M. Safi, M. Soufiaoui, J. Mol. Catal. A.: Chem. 237 (2005) 259-266; (c) M. Pasto, A. Riera, M. Pericas, Eur. J. Org. Chem. (2002) 2337-2341.

10. M. Leautey, P. Jubault, X. Pannexoucke, J.-C. Quirion, Eur. J. Org. Chem. (2003) 3761-3765.

11. (a) A. Bogevig, I. M. Pastor, H. Adolfsson, Chem. Eur. J. 10 (2004) 294-302; (b) D. Carmona, M. P. Lamata, F. Viguri, I. T. Dobrinovich, F. J. Lahoz, L. A. Oro, Adv. Chem. Catal. 344 (2002) 499-502; (c) I. M. Pastor, P. Vastila, H. Adolfsson, Chem. Eur. J. 9 (2003) 4031-4045.

12. (a) Y. Nishibayashi, J. D. Singh, Y. Arikawa, S. Uemura, M. Hidai, J. Organomet. Chem. 531 (1997) 13-18; (b) A. Patti, S. Pedotti, Tetrahedron: Asymmetry 14 (2003) 597-602.

13. M. Aydemir, A. Baysal, S. Özkar, L. T. Y›ld›r›m, Polyhedron 30 (2011) 796-804.

14. M. Aydemir, A. Baysal, Polyhedron 29 (2010) 1219- 1224.

15. M. Aydemir, N. Meriç, A. Baysal, B. Gümgüm, M. Toğrul, Y. Turgut, Tetrahedron: Asymmetry 21 (2010) 703-710.

16. D. Cuervo, M. P. Gamasa, J. Gimeno, Chem. Eur. J. 10 (2004) 425-432.

17. M. Aydemir, A. Baysal, B. Gümgüm, Appl. Organometal. Chem. 26 (2012) 1-8.

18. E. Encarnacion, J. Pons, R. Yanez, J. Ros, Inorg. Chim. Acta 358 (11) (2005) 3272-3276.

19. R. Noyori, M. Yamakawa, S. Hashiguchi, J. Org. Chem. 66 (24) (2001) 7931 7944.

20. M. Aydemir, F. Durap, A. Baysal, N. Meriç, A. Bulda, B. Gümgüm, S. Özkar, L. T. Yıldırım, J. Molecular Catal. A: Chemical 326 (2010) 75 81.

21. A. D. Burrows, M. F. Mahon, M. T. Palmer, J. Chem. Soc., Dalton Trans. (2000) 1669-1677.

22. M. Aydemir, N. Meric, A. Baysal, J. Organomet. Chem. 720 (2012) 38-45.

23. M. Aydemir, A. Baysal, N. Meric, B. Gumgum J. Organomet. Chem. 694 (2009) 2488 2492.

24. R. Le Lagadec, L. Rubio, L. Alexandrova, R. Toscano, E. V. Ivanova, R. Meskys, V. Laurinavicius, M. Pfeffer, A. D. Ryabov, J. Organomet. Chem. 689 (2004) 4820-4832.

25. A. D. Ryabov, V. S. Kurova, V. Ekaterina, R. Ivanova, R. Le Lagadec, L. Alexandrova, Anal. Chem. 77 (2005) 1132-1139.

26. M. Aydemir, A. Baysal, N. Meric, C. Kayan, B. Gümgüm, S. Özkar, E. Sahin J. Organomet. Chem. 696 (2011) 2584-2588.

27. A. M. Maj, K. M. Pietrusiewicz, I. Suisse, F. Agbossou, A. Mortreux, J. Organomet. Chem. 626 (2001) 157- 160.

28. J. X. Gao, X. D. Yi, P. P. Xu, C. -L. Tang, H. L. Wan, T. Ikariya, J. Organometal. Chem. 592 (1999) 290-295.

29. J. X. Gao, H. Zhang, X. D. Yi, P. P. Xu, C. L. Tang, H. L. Wan, K. R. Tsai, T. Ikariya, Chirality 12 (2000) 383-388.

30. R. Noyori, T. Ohkuma, Angew. Chem. Int. Ed. Engl. 40 (2001) 40-73.

31. J. Canivet, G. Labat, H. Stockli-Evans, G. Süss-Fink, Eur. J. Inorg. Chem. (2005) 4493-4500.

32. P. Stepnicka, J. Ludvíc, J. Canivet, G. Süss-Fink, Inorg. Chim. Acta 359 (2006) 2369-2374.

33. P. Dani, T. Karlen, R. A. Gossage, S. Gladialli, F. G. Koten, Angew. Chem. Int. Ed. Engl. 39 (2000) 743-745.

34. Z. Fei, R. Scopelliti, P.J. Dyson, Inorg. Chem. 42 (2003) 2125-2130.

35. Z. Fei, R. Scopelliti, P.J. Dyson, Eur. J. Inorg. Chem. (2004) 530-537.

36. S. Berger, S. Braun, H. O. Kolinowski, NMRSpektroskopie von Nichtmetallen Band 3, 31P NMR Spektroskopie, Georg Theime Verlag, Stuttgart, New York, (1993).

37. R. A. Zelonka, M.C. Baird, J. Organomet. Chem. 35 (1972) C43-C46.

38. M. A. Bennet, A. K. Smith, J. Chem. Soc. Dalton Trans. (1974) 233-241.

39. M. A. Bennet, T. N. Huang, T. W. Matheson, A. K. Smith, Inorg. Synth. 7 (1982) 74-78.