Aniline based aminophosphine and cationic bis phosphino amine Ru II complexes: Investigation of catalytic activity in transfer hydrogenation of ketones

Year 2013, Volume: 2 Issue: 1, 20 - 27, 01.06.2013

Cezmi Kayan Nermin Meriç Murat Aydemir Akın Baysal Hamdi Temel

Abstract

Hydrogen transfer reduction processes are attracting increasing interest from synthetic chemists in viewof their operational simplicity. For this aim, a series of Ru II complexes with the NPP and NHP ligandswere synthesized starting from the complex [Ru η6-p-simen µ-Cl Cl]2. The complexes were fullycharacterized by analytical and spectroscopic methods. Complexes 1-4 catalyze the transfer hydrogenationof a variety of simple alkyl and aryl alkyl ketones to secondary alcohols in the presence of iso-PrOH as thehydrogen source. Notably 3 acts as an excellent catalyst giving the corresponding alcohols in excellentconversions up to 99% TOF:198 h-1

Keywords

Aminophosphine, Bis phosphino amine, Transfer hydrogenation, Ruthenium, Catalysis, Ketone

Anilin temelli aminofosfinler ve katyonik bis fosfino amin Ru II kompleksleri: Ketonların transfer hidrojenasyonundaki katalitik aktiviteleri

Abstract

Hidrojen transfer indirgenme reaksiyonu, ifllem kolaylığı avantajından dolayı sentez alanında çalıflankimyacıların ilgisini çekmektedir. Bu bağlamda, [Ru η-p-simen µ-Cl Cl]2 kompleksinden yola çıkarakNPP ve NHP ligandlarının bir dizi Ru II kompleksi sentezlendi ve bu kompleksler analitik ve spektroskopikmetotlarla tam olarak karakterize edildi. 1 - 4 kompleksleri hidrojen kaynağı olarak izopropil alkol varlığındabirçok alkil ve aril alkil ketonların sekonder alkollere transfer hidrojenasyonunu katalizlemektedir. Özellikle3 nolu kompleks mükemmel bir katalizör olarak davranmakta ve ilgili alkolleri % 99 a varan dönüflümlerlesağlamaktadır TOF:198 h-1

Keywords

Aminofosfin, Bis fosfino amin, Transfer hidrojenasyon, Rutenyum, Kataliz, Keton

References

• 1. S. Gladiali, G. Mestroni, Transition Metal for Organic Synthesis (Eds.: M. Beller. C. Bolm), Wiley-VCH, Weinheim 2 (1998) 97-119.
• 2. H. Siegel. V. Himmele, Angew. Chem. Int. Ed. Engl. 92 (1980) 182-187.
• 3. C. Botteghi, S. Paganelli, A. Schionato, M. Marchetti, Chirality 3 (1991) 355-369.
• 4. H. Jiang, Q. D. Qiao, H. Gong, React. Kinet. Catal. Lett. 65 (1998) 193-197.
• 5. J. S. M. Samec, Jan-E. Backvall, Chem. Eur. J. 8 (2002) 2955-2961.
• 6. A. Del Zotto, W. Baratta, M. Ballico, E. Herdtweck, P. Rigo, Organometallics 26 (2007) 5636-5642.
• 7. K.G. Gaw, M.B. Smith, A.M.Z. Slawin, New J. Chem. 24 (2000) 429-435.
• 8. N. Biricik, F. Durap, B. Gumgum, Z. Fei, R. Scopelliti, Transition Met. Chem. 32 (7) (2007) 877- 883.
• 9. M. Aydemir, F. Durap, A. Baysal, O. Akba, B. Gumgum, S. Özkar, L.T. Yıldırım, Polyhedron 28 (2009) 2313-2320.
• 10. M. Necas, M.R.J. Foreman, J. Marek, J. D. Woollins, J. Novosad, New J. Chem. 25 (2001) 1256-1263.
• 11. M. Aydemir, A. Baysal, J. Organomet. Chem. 695 (2010) 2506-2511.
• 12. M. Aydemir, A. Baysal, Polyhedron 29 (2010) 1219- 1224.
• 13. M. S. Balakrishna, K. Ramaswarmy, R.M. Abhyankar, J. Organomet. Chem. 560 (1998) 131- 136.
• 14. A. M. Maj, K.M. Michal, I. Suisse, F. Agbossou, A. Mortreux, Tetrahedron: Asymmetry 10 (1999) 831- 835.
• 15. 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.
• 16. A. D. Ryabov, V. S. Kurova, V. Ekaterina, R. Ivanova, R. Le Lagadec, L. Alexandrova, Anal. Chem. 77 (2005) 1132-1139.
• 17. M. Aydemir, A. Baysal, N. Meric, C. Kayan, B. Gümgüm, S. Özkar, E. Sahin, J. Organomet. Chem. 696 (2011) 2584-2588.
• 18. J. X. Gao, X. D. Yi, P. P. Xu, C. -L. Tang, H. L. Wan, T. Ikariya, J. Organometal. Chem. 592 (1999) 290-295.
• 19. 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.
• 20. J.-S. Chen, Y.-Y. Li, Z.-R. Dong, B.-Z. Li, J.-X. Gao, Tetrahedron Lett. 45 (2004) 8415-8418.
• 21. M. A. Bennet, A. K. Smith, J. Chem. Soc. Dalton Trans. (1974) 233-241.
• 22. M. A. Bennet, T. N. Huang, T. W. Matheson, A. K. Smith, Inorg. Synth. 7 (1982) 74-78.