Synthesis and properties of a silyl(silylene)ruthenium complex: activation barrier of the Ru=Si bond rotation and facile replacement of the methyl groups with alkoxy groups of a silyl ligand

Organometallics

Volumn 28, Issue 14, 2009, Pages 3963-3965

  Hashimoto, Hisako ^a   Sato, Jun ^a   Tobita, Hiromi ^a  

^a TOHOKU UNIVERSITY   (Japan)

Author keywords

[No Author keywords available]

Indexed keywords

ACTIVATION BARRIERS; ACTIVATION PARAMETER; ALKOXY GROUP; ALKOXYLATION; BOND ROTATIONS; FLUXIONAL BEHAVIOR; H NMR SPECTRA; HIGH YIELD; LINE-SHAPE ANALYSIS; METHYL GROUP; ROOM TEMPERATURE; RUTHENIUM COMPLEXES; SI-C BOND; SILYL LIGANDS; SILYLENE; VARIABLE TEMPERATURE;

ACTIVATION ANALYSIS; CHELATION; HYDROCARBONS; IRON COMPOUNDS; LIGANDS; NUCLEAR MAGNETIC RESONANCE SPECTROSCOPY; ROTATION; RUTHENIUM; RUTHENIUM COMPOUNDS; SILANES; SYNTHESIS (CHEMICAL);

SILICON;

EID: 67651039725     PISSN: 02767333     EISSN: None     Source Type: Journal    
DOI: 10.1021/om900177z     Document Type: Article

References (35)

1. (a) Tilley, T. D. In The Chemistry of Organic Silicon Compounds; Patai, S., Rappoport, Z., Eds.; John Wiley & Sons: New York, 1989; Chapter 24.
2. (b) Eisen, M. S. In The Chemistry of Organic Silicon Compounds Vol. 2; Rappoport, Z., Apeloig, Y, Eds.; John Wiley & Sons: New York, 1998; Chapter35.
3. (c) Ogino,H. Chem. Rec. 2002, 2, 291.
4. (d) Okazaki,M.;Tobita, H.; Ogino, H. J. Chem. Soc, Dalton Trans. 2003, 493, and references therein.
5. (a) Gehrhus, B.; Hitchcock, P. B.; Lappert, M. F.; Maciejewski, H. Organometallics 1998, 17, 5599.
6. (b) Avent, A. G.; Gehrhus, B.; Hitchcock, P. B.; Lappert, M. F.; Maciejewski, H. J. Organomet. Chem. 2003, 686, 321.
7. (a) Ueno, K.; Asami, S.; Watanabe, N.; Ogino, H. Organometallics 2002, 21, 1326.
8. (b) Hirotsu, M.; Nunokawa, T.; Ueno, K. Organometallics 2006, 25, 1554.
9. (a)Tobita, H.; Matsuda, A.; Hashimoto, H.; Ueno, K.; Ogino, H. Angew. Chem., Int. Ed. 2004, 43, 221.
10. (b) Hashimoto, H.; Matsuda, A.; Tobita, H. Chem. Lett. 2005, 1374.
11. (c) Hashimoto, H.; Matsuda, A.; Tobita, H. Organometallics 2006, 25, 472.
12. (a) Pannell, K. H.; Cervantes, J.; Hernandez; Cassias, J.; Vincenti, S. Organometallics 1986, 5, 1056.
13. (b) Tobita, H.; Ueno, K.; Ogino, H. Chem. Lett. 1986, 1777.
14. (c) Ueno, K.; Tobita, H.; Ogino, H. Chem. Lett. 1990, 369.
15. (d) Sharma, H. K.; Pannell, K. H. Chem. Rev. 1995, 95, 1351. (6) Jose, R.; Maitlis, P. M. J. Chem. Soc, Chem. Commun. 1986, 862.
16. For the related works, there are a few examples of photoinduced mono- or dialkoxylation of alkyl groups with alcohol and hydroxylation of alkyl groups on the silyl ligands with water or strong base under heating conditions. For photoinduced alkoxylation reaction, see: (a) Ueno, K.; Seki, S.; Ogino, H. Chem. Lett. 1993, 2159.
17. For hydroxylation reactions, see: (b) Akhrem, I. S.; Chistovalova, N. M.; Mysov, E. I.; Vol'pin, M. E. J. Organomet. Chem. 1974, 72, 163.
18. (c) Albrecht, M.; Kwok, W.-H.; Lu, G.-L.; Rickard, C. E. F.; Roper, W. R.; Salter, D. M.; Wright, L. J. Inorg. Chim. Acta 2005, 358, 1407.
19. Iwata, M.; Okazaki, M.; Tobita, H. Organometallics 2006, 25, 6115.
20. (a) Straus, D. A.; Grumbine, S. K.; Tilley, T. D. J. Am. Chem. Soc. 1990, 112, 7801.
21. (b)Grumbine, S. K.; Mitchell, G. P.; Straus, D. A.; Tilley, T. D. Organometallics 1998, 17, 5607.
22. (c) Dysard, J. M.; Tilley, T. D. Organometallics 2000, 19, 4726.
23. (d) Schmedake, T. A.; Haaf, M.; Paradise, B. J.; Millevolte, A. J.; Powell, D. R.; West, R. J. Organomet. Chem. 2001, 636, 17.
24. (e) Ochiai, M.; Hashimoto, H.; Tobita, H. Angew. Chem., Int. Ed. 2007, 46, 8192.
25. For the details, see Supporting Information.
26. w = 0.1004 for all data, 6879 unique reflections. Crystallographic Information has been deposited with the Cambridge Crystallography Data Centre: CCDC 698346 (2).
27. Based on a survey of the Cambridge Structural Database, CSD verison 5.29 (November 2007).
28. Rotation barrier for the two mesityl groups around the Si-C (mesityl) single bond could be derived from the analysis of the o-Me or m-H signals. However, unfortunately, sufficient line-shape analysis was not possible for the o-Me signals, because four o-Me signals coalesced around 361 K, but, above this temperature, the very broad signal did not become sharp enough for the analysis even at 380 K, which was the upper limit of temperature due to the boiling point of the solvent. For the m-H signals, we were not able to get good visual line fitting. It seems that the long-range couplings between the m-protons in the mesityl groups affect the line width, and we could not estimate it exactly, even though we tested various coupling constants.
29. (a) Nakatsuji, H.; Usio, J.; Yonezawa, T. J. Organomet. Chem. 1983, 258, C1.
30. (b) Márquez, A.; Sanz, J. F. J. Am. Chem. Soc. 1992, 114, 2903.
31. (a) Grumbine, S. K.; Tilley, T. D.; Arnold, F. P.; Rheingold, A. L. J. Am. Chem. Soc. 1994,116,5495.
32. (b) Mork, B. V; Tilley, T. D.; Schultz, A. J.; Cowan, J. A. J. Am. Chem. Soc. 2004, 126, 10428.
33. (a) Ueno, K.; Masuko, A.; Ogino, H. Organometallics 1997,16, 5023.
34. (b) Wada, H.; Tobita, H.; Ogino, H. Chem. Lett. 1998, 993.
35. (c) Ueno, K.; Masuko, A.; Ogino, H. Organometallics 1999, 18, 2694.