A coordinatively unsaturated species with an agostic C-H interaction, [(κ4-TpiPr)Ru(dppe)]OSO2CF3, and its addition reaction

Organometallics

Volumn 18, Issue 14, 1999, Pages 2571-2573

  Takahashi, Yoshiaki ^a   Hikichi, Shiro ^a   Akita, Munetaka ^a   Moro oka, Yoshihiko ^a  

^a TOKYO INSTITUTE OF TECHNOLOGY   (Japan)

Author keywords

[No Author keywords available]

Indexed keywords

EID: 0001658215     PISSN: 02767333     EISSN: None     Source Type: Journal    
DOI: 10.1021/om990250s     Document Type: Article

References (26)

1. (a) Collman, J. P.; Hegedus, L. S.; Norton, J. R.; Finke, R. J. Principles and Applications of Organometallic Chemistry, 2nd ed.; University Science Book: Mill Valley, CA, 1987.
2. (b) Crabtree, R. H. The Organometallic Chemistry of the Transition Metals, 2nd ed.; Wiley: New York, 1994.
3. (c) Yamamoto, A. Organotransition Metal Chemistry: Wiley: New York, 1986.
4. (d) Elschenbroich, C.; Salzer, A. Organometallics, 2nd ed.; VCH: Weinheim, Germany, 1992.
5. R systems are as follows. Rh-diene: (a) Akita, M.; Ohta, K.; Takahashi, Y.; Hikichi, S.; Moro-oka, Y. Organometallics 1997, 16, 4121.
6. Ru-aqua: (b) Takahashi, Y.; Akita, M.; Hikichi, S.; Moro-oka, Y. Inorg. Chem. 1998, 37, 3186.
7. Ru-diene: (c) Takahashi, Y.; Akita, M.; Hikichi, S.; Moro-oka, Y. Organometallics 1998, 17, 4884.
8. Pd-OOR: (d) Akita, M.; Miyaji, T.; Hikichi, S.; Morooka, Y. J. Chem. Soc., Chem. Commun. 1998, 1005.
9. Co-OOR: (e) Hikichi, S.; Komatsuzaki, H.; Akita, M.; Moro-oka, Y. J. Am. Chem. Soc. 1998, 720, 4699.
10. Co, Ni-oxo: (f) Hikichi, S.; Yoshizawa, M.; Sasakura, Y.; Akita, M.; Moro-oka, Y. J. Am. Chem. Soc. 1998, 120, 10567.
11. Fe, Co, Ni-alkyl: (g) Akita, M.; Shirasawa, N.; Hikichi, S.; Moro-oka, Y. J. Chem. Soc., Chem. Commun. 1998, 973.
12. (h) Shirasawa, N.; Akita, M.; Hikichi, S.; Moro-oka, Y. J. Chem. Soc., Chem. Commun. 1999, 417.
13. Mn-OO(R): (i) Komatsuzaki, H.; Sakamoto, N.; Satoh, M.; Hikichi, S.; Akita, M.; Moro-oka, Y. Inorg. Chem. 1998, 37, 6554.
14. iPr = 3,5-diisopropylpyrazolyl; OTf = trifluoromethanesulfonate.
15. The synthesis of 1 was reported in ref 2b.
16. (a) A closely related labile species with the parent Tp ligand was studied by Kirchner et al. However, the coordinatively unsaturated intermediate could not be detected, presumably due to the lack of substituents which would interact with the unsaturated site. Trimmel, G.; Slugovc, C.; Wiede, P.; Mereiter, K.; Sapunov, V. N.; Schmid, R.; Kirchner, K Inorg. Chem. 1997, 36, 1076.
17. 2Cl, which showed the methyl signal of the isopropyl substituent attached to the phosphorus atom at σ -0.23, but no conclusive evidence was obtained. Tenorio, M. A. J.; Tenorio, M. J.; Puerta, M. C.; Valerga, P. J. Chem. Soc., Dalton Trans. 1998, 3601.
18. 2Ru (3a· acetone): C, 58.58; H, 6.72; N, 6.83. Found: C, 58.32; H, 6.99; N, 6.99.
19. (a) Brookhart, M.; Green, M. L. H. J. Organomet. Chem. 1983, 250, 395.
20. (b) Brookhart, M.; Green, M. L. H.; Wong, L. L. Prog. Inorg. Chem. 1988, 36, 1.
21. 2Ru: C, 58.22; H, 6.33; N, 7.54. Found: C, 57.70; H, 6.22; N, 7.41.
22. 0), 697 parameters; R1 = 0.088, wR2 = 0.229.
23. The second closest interaction between the ruthenium center and the proximal isopropyl groups is Ru1-C24 = 3.331(6) Å, and the others are in the range from 3.918(7) Å (C34) to 5.063(9) Å (C36).
24. C ∼8.5) was observed at -95 °C, the coupling constants could not be analyzed due to the broad peak shape.
25. 2): C, 53.84; H, 5.91; N, 9.13. Found: C, 53.58; H, 5.78; N, 8.92.
26. 2.