Hayati TÜRKMEN, Aylin ATİK, Lütfiye GÖK PEZÜK

N-heterocyclic carbenes bearing a naphthyl substituent and their metal complexes: synthesis, structure, and application in catalytic transfer hydrogenation

A series of unsymmetrical imidazolinium bromides (3a d) bearing naphthyl and benzyl groups (R = CH2 C6 H2 (CH3)3 -2,4,6 (a); CH2 C6 H(CH3)4 -2,3,5,6 (b); CH2 C6 (CH3)5 (c); CH2 C6F5 (d)) at the N1 and N3 positions were successfully synthesized. [RuCl 2 (NHC)(p-cymene)] (NHC= N-heterocyclic carbene) complexes (4a d) were prepared by the reaction of [RuCl 2(p-cymene)] 2 with imidazolinium salts (3a d). The new salts (3a d) and their ruthenium(II) complexes (4a d) were characterized by 1 H, 13 C, 19F NMR, and elemental analysis. The ruthenium(II) complexes (4a d) were employed as catalysts for the transfer hydrogenation (TH) of ketones in the presence of KOH using 2-propanol as a hydrogen source and the results were compared. The best results in the transfer hydrogenation of ketones were obtained with 4b. [MCl(NHC)L] (M = Ir, L = Cp ∗ ) (5b), cod (6b); M = Rh, L= Cp ∗ (5b ), and cod (6b ) complexes were prepared and investigated in the TH of ketones. The reactivity of Rh complexes in comparison to those of Ir also appears to be somewhat better. The catalysis appears to be homogeneous.

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1. Wanzlick, H. W.; Kleiner, H. J. Angew. Chem. 1961, 73, 493-498.
2. Ofele, K. ¨ J. Organomet. Chem. 1968, 12, 42-43.
3. Lappert, M. F. J. Organomet. Chem. 1988, 358, 185-213.
4. Arduengo, A. J.; Harlow, R. L.; Kline, M. J. Am. Chem. Soc. 1991, 113, 361-363.
5. Hahn, F. E.; Jahnke, M. C. Angew. Chem. Int. Ed. Engl. 2008, 47, 3122-3172.
6. Glorius, F. N-Heterocyclic Carbenes in Transition Metal Catalysis. Springer Verlag: Berlin, Germany, 2007.
7. Nolan, S. P. N-Heterocyclic Carbenes in Synthesis. Wiley-VCH: Weinheim, Germany, 2006.
8. Diez-Gonzalez, S.; Nolan, S. P. Coord. Chem. Rev. 2007, 251, 874-883.
9. Herrmann, W. A. Angew. Chem. Int. Ed. Engl. 2002, 41, 1290-1309.
10. Schuster, O.; Yang, L.; Raubenheimer, H. G.; Albrecht, M. Chem. Rev. 2009, 109, 3445- 3478.
11. Kantchev, E. A. B.; OBrien, J.; Organ, M. G. Angew. Chem. Int. Ed. 2007, 46, 2768-2813.
12. G¨urb¨uz, N.; Karaca, E. O.; ¨ Ozdemir, ¨ ˙I.; C¸ etinkaya, B. Turk. J. Chem. 2015, 39, 1115-1157.
13. Trnka, T. M.; Grubbs, R. H. Acc. Chem. Res. 2001, 34, 18-29.
14. Lee, H. M.; Jiang, T.; Stevens, L. E. D.; Nolan, S. P. Organometallics 2001, 20, 1255- 1258.
15. Powell, M. T.; Hou, D.; Perry, M. C.; Cui, X.; Burgess, K. J. Am. Chem. Soc. 2001, 123, 8878-8879.
16. Perry, M. C.; Cui, X.; Hou, D. R.; Reibenspies, H. J. J. Am. Chem. Soc. 2003, 125, 113- 123.
17. Noyori, R.; Hashiguchi, S. Acc. Chem. Res. 1997, 30, 97-102.
18. Gladiali, S.; Alberico, E. Chem. Soc. Rev. 2006, 35, 226-236.
19. Ikariya, T.; Blacker, A. J. Acc. Chem. Res. 2007, 40, 1300-1308.
20. Clapham, S. E.; Hadzovic, A.; Morris, R. H. Coord. Chem. Rev. 2004, 248, 2201-2237.
21. Samec, J. S. M.; B¨ackvall, J. E.; Andersson, P. G.; Brandt, P. Chem. Soc. Rev. 2006, 35, 237-248.
22. Alfonsi, K.; Colberg, J.; Dunn, P. J.; Fevig, T.; Jennings, S.; Johnson, T. A.; Kleine, H. P.; Knight, C.; Nagy, M. A.; Perry, D. A.; et al. Green Chem. 2008, 10, 31-36.
23. Canivet, J.; Lapat, G.; Stoeckli- Evans, H.; S¨uss-Fink, G. Eur. J. Inorg. Chem. 2005, 4493-4500.
24. Baratta, W.; Chelucci, G.; Gladiali, S., Siega, K.; Toniutti, M.; Zanette, M.; Zangrando, E.; Rigo, P. Angew. Chem. Int. Ed. 2005, 44, 6214-6219.
25. Baratta, W.; Herdtweck, E.; Siega, K.; Toniutti, M.; Rigo, P. Organometallics 2005, 24, 1660-1669.
26. Del Zotto, A.; Baratta, W.; Ballico, M.; Herdtweck, E.; Rigo, P. Organometallics 2007, 26, 5636-5642.
27. Hillier, A. C.; Lee, H. M.; Stevens, E. D.; Nolan, S. P. Organometallics 2001, 20, 4246-4252.
28. T¨urkmen, H.; Pape, T.; Hahn, F. E.; C¸ etinkaya, B. Organometallics 2008, 27, 571-575.
29. T¨urkmen, H.; Pape, T.; Hahn, F. E.; C¸ etinkaya, B. Eur. J. Inorg. Chem. 2008, 36, 5418- 5423.
30. G¨ulcemal, S.; Daran, J. C.; C¸ etinkaya, B. Inorg. Chim. Acta 2011, 365, 264-268.
31. Wylie, W. N. O.; Lough, A. J.; Morris, R. H. Organometallics 2012, 31, 2137-2151.
32. Ozdemir, ¨ ˙I.; Ya¸sar, S.; C¸ etinkaya, B. Trans. Metal Chem. 2005, 30, 831-835.
33. Yigit, M.; Yigit, B.; Ozdemir, ¨ ˙I.; C¸ etinkaya, E.; C¸ etinkaya, B. Appl. Organomet. Chem. 2006, 20, 322-327.
34. G¨urb¨uz, N.; Ya¸sar, S.; Ozcan, E. ¨ O.; ¨ Ozdemir, ¨ ˙I.; C¸ etinkaya, B. Eur. J. Inorg. Chem. 2010, 3051-3056.
35. Oru¸c, Z. ˙I.; G¨ok, L.; T¨urkmen, H.; S¸ahin, O.; B¨uy¨ukg¨ung¨or, O.; Cetinkaya, B. J. Organomet. Chem. 2016, 807, 36-44.
36. Kırkar, B. T.; T¨urkmen, H.; Kani, ˙I.; C¸ etinkaya, B. Tetrahedron 2012, 68, 8655-8662.
37. T¨urkmen, H.; Kani, ˙I.; C¸ etinkaya, B. Eur. J. Inorg. Chem. 2012, 4494-4499.
38. T¨urkmen, H. Appl. Organometal. Chem. 2012, 26, 731-735.
39. G¨ok, L.; T¨urkmen, H. Tetrahedron 2013, 69, 10669-10674.
40. Marr, A. C.; Pollock, C. L.; Saunders, G. C. Organometallics 2007, 26, 3283-3285.
41. Gnanamgari, D.; Sauer, E. L. O.; Schley, N. D.; Butler, C.; Incarvito, C. D.; Crabtree, R. H. Organometallics 2009, 28, 321-325.
42. Gong, X.; Zhang, H., Li, X. Tetrahedron Lett. 2011, 52, 5596-5600.
43. G¨ulcemal, S. Appl. Organometal. Chem. 2012, 26, 246-251.
44. Zinner, S. C.; Rentzsch, C. F., Herdtweck, E.; Herrmann, W. A.; K¨uhn, F. E. Dalton Trans. 2009, 7055-7062.
45. Hillier, A. C.; Lee, H. M.; Stevens, E. D.; Nolan, S. P. Organometallics 2001, 20, 4246- 4252.
46. Cortez, N. A.; Aguirre, G.; Parra-Hake, M.; Somanathan, R. Tetrahedron Lett. 2009, 50, 2228-2231.
47. Wu, X.; Xiao, J. Chem. Commun. 2007, 46, 2449-2466.
48. Raja, M. U.; Ramesh, R.; Ahn, K. H. Tetrahedron Lett. 2009, 50, 7014-7017.
49. Foley, P.; DiCosimo, R.; Whitesides, G. M. J. Am. Chem. Soc. 1980, 102, 6713-6725.
50. Anton, D. R.; Crabtree, R. H. Organometallics 1983, 2, 855-859.
51. Eberhard, M. R. Org. Lett. 2004, 6, 2125-2128.
52. Widegren, J. A.; Finke, R. G. J. Mol. Catal. A: Chem. 2003, 198, 317-341.
53. Bennett, M. A.; Smith, A. K. J. Chem. Soc., Dalton Trans. 1974, 233-241.
54. Lin, Y.; Nomiya, K.; Finke, R. G. Inorg. Chem. 1993, 32, 6040-6045.
55. Giordano, G.; Crabtree, R. H. Inorganic Synthesis 1990, 28, 90-92.
56. Maitlis, P. M. Acc. Chem. Res. 1978, 11, 301-307.