Synthesis of (Pentamethylcyclopentadienyl)tantalum sulfido complexes via C-S bond cleavage of triphenylmethanethiolate and formation of a novel trithioborato ligand

Organometallics

Volumn 16, Issue 3, 1997, Pages 307-309

  Kawaguchi, Hiroyuki ^a   Tatsumi, Kazuyuki ^a  

^a NAGOYA UNIVERSITY   (Japan)

Author keywords

[No Author keywords available]

Indexed keywords

EID: 0001414483     PISSN: 02767333     EISSN: None     Source Type: Journal    
DOI: 10.1021/om960864m     Document Type: Article

References (36)

1. (a) Herrmann, W. A. Angew. Chem., Int. Ed. Engl. 1986, 25, 56-76.
2. (b) Müller, A.; Diemann, E. Adv. Inorg. Chem. 1987, 31, 89-122.
3. (c) Wachter, J. Angew. Chem., Int. Ed. Engl. 1989, 28, 1613-1626.
4. Recent examples of early-transition-metal complexes containing the M=S bond are shown in the following references: (a) Carney, M. J.; Walsh, P. J.; Hollander, F. J.; Bergman, R. G. Organometallics 1992, 11, 761-777. (b) Howard, W. A.; Parkin, G. Organometallics 1993, 12, 2363-2366. (c) Howard, W. A.; Parkin, G. J. Organomet. Chem. 1994, 472, C1-C4. (d) Mandimutsira, B. S.; Chen, S.-J.; Demadis, K. D.; Coucouvanis, D. Inorg. Chem. 1995, 34, 2267-2268.
5. Recent examples of early-transition-metal complexes containing the M=S bond are shown in the following references: (a) Carney, M. J.; Walsh, P. J.; Hollander, F. J.; Bergman, R. G. Organometallics 1992, 11, 761-777. (b) Howard, W. A.; Parkin, G. Organometallics 1993, 12, 2363-2366. (c) Howard, W. A.; Parkin, G. J. Organomet. Chem. 1994, 472, C1-C4. (d) Mandimutsira, B. S.; Chen, S.-J.; Demadis, K. D.; Coucouvanis, D. Inorg. Chem. 1995, 34, 2267-2268.
6. Recent examples of early-transition-metal complexes containing the M=S bond are shown in the following references: (a) Carney, M. J.; Walsh, P. J.; Hollander, F. J.; Bergman, R. G. Organometallics 1992, 11, 761-777. (b) Howard, W. A.; Parkin, G. Organometallics 1993, 12, 2363-2366. (c) Howard, W. A.; Parkin, G. J. Organomet. Chem. 1994, 472, C1-C4. (d) Mandimutsira, B. S.; Chen, S.-J.; Demadis, K. D.; Coucouvanis, D. Inorg. Chem. 1995, 34, 2267-2268.
7. Recent examples of early-transition-metal complexes containing the M=S bond are shown in the following references: (a) Carney, M. J.; Walsh, P. J.; Hollander, F. J.; Bergman, R. G. Organometallics 1992, 11, 761-777. (b) Howard, W. A.; Parkin, G. Organometallics 1993, 12, 2363-2366. (c) Howard, W. A.; Parkin, G. J. Organomet. Chem. 1994, 472, C1-C4. (d) Mandimutsira, B. S.; Chen, S.-J.; Demadis, K. D.; Coucouvanis, D. Inorg. Chem. 1995, 34, 2267-2268.
8. (a) Leverd, P. C.; Lance, M.; Vigner, J.; Nierlich, M.; Ephritikhine, M. J. Chem. Soc., Dalton Trans. 1995, 237-244.
9. (b) Coucouvanis, D.; Hadjikyriacou, A.; Lester, R.; Kanatzidis, M. G. Inorg. Chem. 1994, 33, 3645-3655.
10. (a) Kawaguchi, H.; Tatsumi, K. J. Am. Chem. Soc., 1995, 117, 3885-3886.
11. (b) Tatsumi, K.; Sekiguchi, Y.; Nakamura, A.; Cramer, R. E.; Rupp, J. J. J. Am. Chem. Soc. 1986, 108, 1358-1359.
12. (c) Tatsumi, K.; Kawaguchi, H.; Matsubara, I.; Nakamura, A.; Miki, K.; Kasai, N. Inorg. Chem. 1993, 32, 2604-2606.
13. 3 (5.57 mmol) in THF (20 mL). The mixture immediately became yellow and homogeneous. It was stirred for 1 h at room temperature. After removal of the solvent, the residue was extracted with benzene (60 mL), after which the benzene was evaporated at reduced pressure. The resulting yellow solid was dissolved in DME. Cooling the solution produced 1 as yellow crystals (1.04 g, 58%).
14. 3 were isolated, and they were characterized by elemental analyses for C, H, S, and Cl and also by IR spectra.
15. w = 0.041 (GOF = 1.93).
16. (a) Coucouvanis, D.; Chen, S.-J.; Mandimutsira, B. S.; Kim, C. G. Inorg. Chem. 1994, 33, 4429-4430.
17. (b) Lee, S. C.; Li, J.; Mitchell, J. C.; Holm, R. H. Inorg. Chem. 1992, 31, 4333-4338.
18. (c) Schreiner, S.; Aleandri, L. E.; Kang, D.; Ibers, J. A. Inorg. Chem. 1989, 28, 392-393.
19. (d) Drew, M. G. B.; Rice, D. A.; Williams, D. M. J. Chem. Soc., Dalton Trans. 1984, 845-848 and references therein.
20. (a) Curnow, O. J.; Curtis, M. D.; Rheingold, A.; Haggerty, B. S. Inorg. Chem. 1991, 30, 4043-4047.
21. (b) Koo, S.-M.; Bergero, R.; Salifoglou, A.; Coucouvanis, D. Inorg. Chem. 1990, 29, 4844-4846.
22. (c) Tatsumi, K.; Matsubara, I.; Inoue, Y.; Nakamura, A.; Miki, K.; Kasai, N. J. Am. Chem. Soc. 1989, 111, 7766-7777.
23. (d) Martin, J. L.; Takats, J. Inorg. Chem. 1975, 14, 1358-1364 and references therein.
24. 3 (0.50 mmol). Workup similar to that in method A above yielded 2 (0.17 g, 39%).
25. 3 (1.69 mmol) was added to 2 (1.10 g, 1.67 mmol). After the mixture was stirred at room temperature for 24 h, the solvent was pumped off, and the yellow residue was extracted with 30 mL of hexane. Concentrating and cooling the extract to -50°C yielded 3 as yellow crystals (0.33 g, 28%).
26. 2S (0.22 g, 74.8 mmol) in THF, and the mixture was stirred at room temperature for 17 h. After removal of the solvent, the residue was extracted with 40 mL of benzene. The solution was evaporated to dryness, and recrystallization of the resulting solid from THF/hexane afforded 4 as light yellow crystals (0.25 g, 56%).
27. Tatsumi, K.; Inoue, Y.; Nakamura, A.; Cramer, R. E.; VanDorne, W.; Gilje, J. W. J. Am. Chem. Soc. 1989, 111, 782-783.
28. Tatsumi, K.; Inoue, Y.; Kawaguchi, H.; Kohsaka, M.; Nakamura, A.; Cramer, R. E.; VanDoorne, W.; Taogoshi, G. J.; Richmann, P. N. Organometallics 1993, 12, 352-364.
29. 4 (13 mg, 0.34 mmol) in THF (10 mL). The mixture was stirred at room temperature for 12 h, during which time the solution gradually changed from yellow to brown. The mixture was centrifuged to remove insoluble solid, followed by concentration until green microcrystals appeared. Standing for 2 days at -20°C gave 36 mg of 5 as green crystals in 62% yield. Recrystallization from THF afforded green platelike crystals of 5 (recovery 70%).
30. 4.
31. Krebs, B. Angew. Chem., Int. Ed. Engl. 1983, 22, 113-134.
32. w = 0.073 (GOF = 1.88).
33. Brunner, H.; Gehart, G.; Nuber, B.; Wachter, J.; Ziegler, M. L. Angew. Chem., Int. Ed. Engl. 1992, 31, 1021-1022.
34. (a) Hofmann, P.; Rösch, N.; Schmidt, H. R. Inorg. Chem. 1986, 25, 4470-4478.
35. (b) Hofmann, P.; Rösch, N. J. Chem. Soc., Chem. Commun. 1986, 843-844.
36. Kwon, D.; Real, J.; Curtis, M. D.; Rheingold, A. L.; Haggerty, B. S. Inorg. Chem. 1992, 31, 3489-3490.