CF3S-Platinum(II) Complexes with Fluorinated Dithioethers. Molecular Structures of [Pt(SCF3)2(RfSCH2CH2SRf)] Rf = C6H4F-2 and C6H4F-3
Ruy Cervantes,1 Ubaldo Duran,1 Sylvain Bernès2 and Hugo Torrens1*
1 Facultad de Química, Universidad Nacional Autónoma de México. Ciudad Universitaria 04510, México D.F., México. Tel/fax (55)56223724, torrens@servidor.unam.mx.
2 Facultad de Ciencias Químicas, Universidad Autónoma de Nuevo León, Ciudad Universitaria, 66451 S. Nicolás de los Garza, Nuevo León, México.
]]> Recibido el 4 de agosto del 2006;
Abstract
This paper describes the synthesis and characterization of the platinum(II) compounds cis-[Pt(SCF3)2(RfSCH2CH2SRf)] Rf = C6F5 1, C6HF4-4 2, C6H4F-2 3, C6H4F-3 4, C6H4F-4 5 and C6H4(CF3)-3 6. Variable temperature 19F NMR spectra of these complexes, show the presence and interconvertion of syn and anti isomers, consistent with a fast flipping of the metalocycle ring and a slow inversion of configuration at the dithioether sulfur atoms. The molecular and crystalline structures of the compounds [Pt(SCF3)2(2-C6H4FSCH2CH2SC6H4F-2)] 3 and [Pt(SCF3)2(3-C6H4FSCH2CH2SC6H4F-3)] 4, solved by X-ray diffraction are also described.
Key words: fluorothiols, fluorothioetheres, platinum, VT-NMR, X-ray.
Resumen
En este artículo se describen la síntesis y caracterización de los compuestos de platino(II) cis-[Pt(SCF3)2(RfSCH2CH2SRf)], Rf = C6F5 1, C6HF4-4 2, C6H4F-2 3, C6H4F-3 4, C6H4F-4 5 y C6H4(CF3)-3 6. Para estos compuestos, los espectros de RMN de 19F obtenidos a diferentes temperaturas, muestran la presencia e interconversión de isómeros syn y anti, consistente con un cambio conformacional rápido del metalociclo y una inversión de configuración lenta en los átomos de azufre del ditioeter. Se describen también las estructuras cristalinas y moleculares de los compuestos [Pt(SCF3)2(2-C6H4FSCH2CH2SC6H4F-2)] 3 y [Pt(SCF3)2(3-C6H4FSCH2CH2SC6H4F-3)] 4, determinadas mediante difracción de rayos-X.
Palabras clave: Fluorotioles, fluorotioéteres, platino RMN-TV, Rayos X.
]]>DESCARGAR ARTÍCULO EN FORMATO PDF
Acknowledgements
The financial support from DGAPA-UNAM-IN119305 and CONACYT-44494-Q are gratefully acknowledged.
References
1. Dance, I.G., Polyhedron 1986, 5, 1037-1104. [ Links ]
2. Blower, J.P.; Dilworth, J.R. Coord. Chem. Rev. 1987, 76, 121-185. [ Links ]
3. García, J.J.; Arévalo, A.; Montiel, V.; Del Río, F.; Quiroz, B.; Adams, H.; and Maitlis, P.M. Organometallics 1997, 16, 3216-3220. [ Links ]
4. Sellmann, D.; Hille, A.; Heinemam, F.W.; Moll, M.; Rösler, A.; Sutter, J.; Brehm, G.; Reiher, M.; Hess, B.A.; Schneider, S. Inorganica Chimica Acta 2003, 348, 194-198. [ Links ]
5. Krebs, B.; Henkel, G. Angew. Chem. Int. Ed. Engl. 1991, 30, 769-788. [ Links ]
6. (a) Imai, S.; Suzuki, S.K.; Fujisawa, K.; Moro-oka, Y. J. Inorg. Biochem. 1997, 67, 60. [ Links ] (b) Roach, M.P.; Franzen, S.; Dang, P.S.H.; Boxer, S.G.; Woodruff, W.H.; Dawson, J.H. J. Inorg. Biochem. 1997, 67, 134. [ Links ] (c) Ruppert, R.; Kreps, B.; Reedijk, J. J. Inorg. Biochem. 1995, 59, 336. [ Links ] (d) Tsagkalidis, W.; Rodewald, D.; Render, D. J. Inorg. Biochem. 1995, 59, 594. [ Links ]
7. (a) Clark, H.C.; Jain, V.K.; Rao, G.S. J. Organomet. Chem. 1985, 279, 181-191. [ Links ] (b) Jain, V.K.; Rao, G.S. Inorg. Chim. Acta 1987, 127, 161-167. [ Links ] (c) Clarke, M.L. Polyhedron 2001, 20, 151-164. [ Links ] (d) Karet, G.B.; Kostiæ, N.M. Inorg. Chem. 1998, 37, 1021-1027. [ Links ]
8. Torres-Nieto, J.; Arévalo, A.; García-Gutiérrez, P.; Acosta-Ramírez, A.; García, J.J. Organometallics 2004, 23, 4534-4536. [ Links ]
9. Torrens, H. Coord. Chem. Rev. 2000, 196, 331-352. [ Links ]
10. a) Rivera, G.; Bernès, S.; Rodríguez de Barbarin, C.; Torrens, H. Inorg. Chem. 2001, 40, 5575-5580 b) Usó [ Links ]n, R.; Forniés, J.; Usón, N.A.; Tomás, M.; Ibañez, M.A. J. Chem. Soc. Dalton Trans. 1994, 401-405. [ Links ] c) Usón, R., Forniés, J.; Falvello, L.R.; Usón, M.A.; Usón, I., Herrero, S. Inorg. Chem. 1993, 32, 1066-1067. [ Links ]
11. Abel, E.W.; Bhargava, S.K.; Orrell, K.G. Prog. Inorg. Chem. 1984, 32, 1-118. [ Links ]
12. Cross, R.J.; Rycroft, D.S.; Sharp, D.W.A.; Torrens, H. J. Chem. Soc., Dalton Trans. 1980, 2434-2441. [ Links ]
13. Shaver, A.; Morris, S.; Turrin, R.; Day, V.M. Inorg. Chem. 1990, 29, 3622-3629. [ Links ]
14. Beck, W.; Tadros, S., Z. Anorg Allg. Chem. 1979, 375, 231. [ Links ] Beck, W.; Stetter, K.H.; Tadros, S.; Schwarzhans, K.E. Chem. Ber. 1967, 100, 3944-3949. [ Links ]
15. Cross, R.J.; Manojlovic-Muir, L.; Muir, K.W.; Rycroft, D.S.; Sharp, D.W.A.; Solomun, T.; Torrens, H. J. Chem. Soc., Chem. Comm. 1976, 291-292. [ Links ]
16. Cross, R.J.; Dalgleish, I.G.; Smith, G.J.; Wardle, R. J. Chem. Soc., Dalton Trans. 1972, 992-999. [ Links ]
17. Bautista, J.; Bertran, A.; Bernès, S.; Duran, U.; Torrens, H. Rev. Soc. Quím. Méx. 2003, 47, 44-52. [ Links ]
]]>18. Dixon, K.R.; Moss, K.C.; Smith, M.A.R. J. Chem. Soc., Dalton Trans. 1973, 1528-1532. [ Links ]
19. Bruno, I.J.; Cole, J. C.; Edgington, P. R.; Kessler, M.; Macrae, C. F.; McCabe, P.; Pearson, J.; Taylor, R. Acta Cryst. 2002, B58, 389-397. [ Links ]
20. Vaska, L.; Peone, J. Chem. Comm. 1971, 418-419. [ Links ]
21. Hunter, W.N.; Muir, K.W.; Sharp, D.W.A. Acta Cryst. 1984, C40, 37-39. [ Links ]
22. Martin, E.; Toledo, B.; Torrens, H.; Lahoz, F.J.; Terreros, P. Polyhedron 1998, 17, 4091-4099. [ Links ]
]]>23. Cano, O.; Leal, J.; Quintana, P.; Torrens, H. Inorg. Chim. Acta 1984, 89, L9-L10. [ Links ]
24. a) Bertran, A.; del Rio, F.; Torrens, H. Sulfur Lett. 1992, 15, 1117. [ Links ] b). Peach, M.E., Can. J. Chem. 1968, 46, 2699-2708. [ Links ] c) Bertran, A.; Garcia, J.; Martin, E.; Sosa, P.; Torrens, H. Rev. Soc. Quím. Méx. 1993, 37, 185-189. [ Links ]
25. Emeleus, H.J.; McDuffie, D.E., J. Chem. Soc. 1961, 2597-2603. [ Links ]
26. Riddick, J.A.; Bunger, W.B.; Sakaro, T.K., Organic Solvents: Physical Properties and Methods of Purification, 4a Ed., Techniques of Chemistry, Vol II, Wiley-Interscience, N.Y. 1970. [ Links ]
]]>27. Sheldrick, G. M. SHELXS97 and SHELXL97. Programs for Solution and Crystal Structure Refinement, University of Göttingen, Göttingen, Germany, 1997. [ Links ]
28. Siemens, XSCANS. Version 2.21. Siemens Analytical X-ray Instruments Inc., Madison, Wisconsin, USA, 1996. [ Links ]
]]>