New ruthenium(II) heteroleptic complexes containing the 4-(2-pyridyl)pyrimidine ligand with amine and amino acid substituents

Abstract

New 4-(2-pyridyl)pyrimidines (L) have been synthesized in high yields by condensing enaminones with the appropriate carboxamidine or guanidine under basic conditions. These asymmetric bidentate diimine ligands coming from a one-step functionalization of amine and amino acid groups were complexed to ruthenium to obtain new heteroleptic complexes of type [Ru(bpy)₂(L)]²⁺. The ligands and complexes have been characterized by usual analytical methods, and the crystallographic study of one complex has been performed. Their spectroscopic and electrochemical properties have been investigated. ZINDO Calculations show that in the MLCT excited state the electron is mainly localized on the pyridylpyrimidine ligand. On the basis of electrochemical data, the first reduction potential of the complexes has been assigned to the redox couple involving this ligand.

References

1. E. Amouyal, Sol. Energy Mater. Sol. Cells, 1995, 38, 249; in Homogeneous Photocatalysis, ed. M. Chanon, Wiley, Chichester, 1997, ch. 8, p. 263; A. Kay and M. Gratzel, Sol Energy Mater. Sol. Cells, 1996, 44, 99; R. Argazzi, C. A. Bignozzi, G. M. Hasselman and G. J. Meyer, Inorg. Chem., 1998, 37, 4533.
2. V. Balzani and F. Scandola, Supramolecular Photochemistry, Ellis Horwood, New York, 1991; A. Hatzidimitriou, A. Gourdon, J. Devillers, J. P. Launay, E. Mena and E. Amouyal, Inorg. Chem., 1996, 35, 2212.
3. J. K. Barton, A. T. Danishefksy and J. M. Goldberg, J. Am. Chem. Soc., 1984, 106, 2172; J. Kelly, A. Tossi, D. McConnel and C. OhUigin, Nucleic Acids Res., 1985, 13, 6017.
4. K. Kalyanasundaram, Coord. Chem. Rev, 1982, 46, 159; A. Juris, V. Balzani, F. Barigelletti, S. Campagna, P. Belser and A. Von Zelewsky, Coord. Chem. Rev., 1988, 84, 85; E. C. Constable, Adv. Inorg. Chem., 1989, 34, 1; Prog. Inorg. Chem., 1994, 42, 67.
5. Y. Kawanishi, N. Kitamura and S. Tazuke, Inorg. Chem., 1989, 28, 2968; F. Casalboni, Q. G. Mulazzani, C. D. Clark, M. Z. Hoffman, P. L. Orizondo, M. W. Perkovic and D. P. Rillema, Inorg. Chem., 1997, 36, 2252.
6. (a) E. Bejan, H. Aït-Haddou, J.-C. Daran and G. G. A. Balavoine, Synthesis, 1996, 1012; (b) E. Amouyal, F. Penaud-Berruyer, D. Azhari, H. Aït-Haddou, C. Fontenas, E. Bejan, J.-C. Daran and G. A. A. Balavoine, New J. Chem., 1998, 22, 373.
7. I. Sasaki, M. Imberdis, A. Gaudemer, B. Drahi, D. Azhari and E. Amouyal, New J. Chem., 1994, 18, 759; D. Esposito, G. Del Vecchio and G. Barone, J. Am. Chem. Soc., 1997, 119, 2606 and refs. therein R. H. Terbrueggen, T. W. Johann and J. K. Barton, Inorg Chem., 1998, 37, 6874.
8. A. Altomare, G. Cascarano, G. Giacovazzo, A. Guagliardi, M. C. Burla, G. Polidori and M. Camalli, SIR 92, a program for automatic solution of crystal structures by direct methods, J. Appl. Crystallogr., 1994, 27, 435.
9. G. M. Sheldrick, SHELXL 97, program for crystal structure refinement, University of Göttingen, 1997.
10. D. J. Watkin, C. K. Prout and L. J. Pearce, CAMERON, Chemical Crystallography Laboratory, University of Oxford, Oxford, 1996.
11. A. D. Bacon and M. C. Zerner, Theor. Chim. Acta, 1979, 53, 21.
12. W. P. Anderson, T. R. Cundari and M. C. Zerner, Int. J. Quantum Chem., 1991, 39, 31.
13. R. F. Abdulla and R. V. Brinkmeyer, Tetrahedron, 1979, 35, 1675.
14. B. Imperiali and S. L. Fisher, J. Am. Chem. Soc., 1991, 113, 8527; B. Imperiali, T. J. Prins and S. T. Fisher, J. Org. Chem., 1993, 58, 1613; M. R. Ghadiri, C. Soares and C. Choi, J. Am. Chem. Soc., 1992, 114, 825; S. R. Wilson, A. Yasmin and Y. Wu, J. Org. Chem., 1992, 57, 6941; P. R. Cheng, S. L. Fisher and B. Imperiali, J. Am. Chem. Soc., 1996, 118, 11349.
15. E. Bejan, H. Aït-Haddou, J.-C. Daran and G. G. A. Balavoine, Eur. J. Org. Chem., 1998, 2907.
16. S. T. Howard, J. Am. Chem. Soc., 1996, 118, 10268.
17. S. J. Milder, Inorg. Chem., 1989, 28, 868.
18. J. N. Spencer, S. W. Barton, K. A. Smith, W. S. Wolbach, J. F. Powell, M. R. Kirschenbaum and D. W. Firth, Can. J. Chem., 1982, 61, 194.
19. R. P. Thummel and F. Lefoulon, Inorg. Chem., 1987, 26, 675.
20. D. P. Rillema, D. G. Taghdiri, D. S. Jones, C. D. Keller, L. A. Worl, T. J. Meyer and H. A. Levy, Inorg. Chem., 1987, 26, 578; H. Ichida, S. Tachiyashiki and Y. Sasaki, Chem. Lett., Chem. Soc. Jpn., 1990, 63, 1299; E. Kimura, S. Wada, M. Shionoya, T. Takahashi and Y. Iitaka, J. Chem. Soc., Chem. Commun., 1990, 397; R. Chotalia, E. C. Constable, M. J. Hannon and D. A. Tocher, J. Chem. Soc., Dalton Trans., 1995, 3571; D. A. Bardwell, F. Barigelletti, R. L. Cleary, L. Flamigni, M. Guardigli, J. C. Jeffery and M. D. Ward, Inorg. Chem., 1995, 34, 2438.
21. G. Calzaferri and R. Rytz, J. Phys. Chem., 1995, 99, 12141; B. J. Coe, D. W. Thompson, C. T. Culbertson, J. R. Schoonover and T. J. Meyer, Inorg. Chem., 1995, 34, 3385.
22. R. P. Thummel, F. Lefoulon and J. D. Korp, Inorg. Chem., 1987, 26, 2370.
23. Y. Kawanishi, N. Kitamura, Y. Kim and S. Tazuke, Sci. Pap. Inst. Phys. Chem. Res. (Jpn.), 1984, 78, 212; A. Vlcek, Chemtracts-Inorg. Chem., 1991, 5, 2144.