Sequential electrophile/nucleophile additions for η2-cyclopentadiene complexes of osmium(II), ruthenium(II), and rhenium(I)

Organometallics

Volumn 15, Issue 26, 1996, Pages 5447-5449

  Spera, Michael L ^a   Martin Chin, R ^a   Winemiller, Mark D ^a   Lopez, Katharine W ^a   Sabat, Michal ^a   Harman, W Dean ^a  

^a UNIVERSITY OF VIRGINIA   (United States)

Author keywords

[No Author keywords available]

Indexed keywords

EID: 0001350942     PISSN: 02767333     EISSN: None     Source Type: Journal    
DOI: 10.1021/om960905e     Document Type: Article

References (27)

1. Brookhart, M.; Volpe, A. F., Jr.; Yoon, J. In Comprehensive Organic Synthesis; Trost, B. M., Ed.; Pergamon Press: Oxford, U.K., 1991; Vol. 4, Chapter 3.5.
2. (a) Pearson, A. J.; Srinivasan, K. J. Org. Chem. 1992, 57, 3965.
3. (b) Brookhart, M.; Noh, S. K.; Timmers, F. J.; Hong, Y. H. Organometallics 1988, 7, 2458.
4. (c) Johnson, B. F. G.; Lewis, J.; Randall, G. L. P. Chem. Commun. 1969, 1273.
5. (a) Johnson, B. F. G.; Lewis, J.; Yarrow, D. J. J. Chem. Soc., Dalton Trans. 1972, 2084.
6. (b) Pearson, A. J. Metallo-organic Chemistry; Wiley: New York, 1985; p 267.
7. (a) Kopach, M. E.; Gonzalez, J.; Harman, W. D. J. Am. Chem. Soc. 1991, 56, 4321.
8. (b) Hodges, L. M.; Gonzalez, J.; Myers, W. H.; Koontz, J. I.; Harman, W. D. J. Org. Chem 1995, 60, 2125.
9. (c) Kolis, S. P.; Gonzales, J.; Bright, L. M.; Harman, W. D. Organometallics 1996, 15, 245.
10. 2 occurs on the uncoordinated portion of butadiene, but this reaction readily occurs for organic olefins. See: Elliot, M. G.; Shepherd, R. E. Inorg. Chem. 1988, 27, 3332.
11. 2+ was previously reported to undergo protonation to form an allyl species; however, nothing was reported about the mechanism. See: Harman, W. D.; Hasegawa, T.; Taube, H. Inorg. Chem. 1991, 30, 453.
12. 2Os: C, 13.15; H, 3.31; N, 10.95. Found: C, 12.96; H, 3.60; N, 10.78.
13. 9Os: C, 12.17; H, 2.81; N, 8.87. Found: C, 11.95; H, 2.47; N, 9.14.
14. w = 0.090, and GOF = 2.46.
15. Exo addition of electrophiles is also observed with aromatic systems bound to pentaammineosmium(II). See ref 4.
16. 2-diene complexes of osmium(II).
17. 13C, DEPT, and NOE.
18. Nucleophiles that react with 2, 3, or 8 include silated enols, hydride, and cyanide reagents. Spera, M. L.; Lopez, K. W.; Harman, W. D. Preliminary results.
19. 3 in acetone and CpH with Zn/Hg amalgam. Yield = 79%. See Supporting Information.
20. 3CN, -40°C) δ 5.18 (m, 1H), 5.02 (m, 1H), 4.75 (br s, 3H), 3.38 (dd, J = 20.2 Hz, 4.9 Hz, 1H), 2.92 (br s, 12H). One proton resonance was not assigned.
21. + are within 200 mV of each other. See ref 17.
22. Chin, R. M.; Dubois, R. H.; Helberg, L. E.; Sabat, M.; Bartucz, T. Y.; Lough, A. J.; Morris, R. H.; Harman, W. D. Manuscript submitted for publication.
23. 2ReS: C, 39.34; H, 4.01; N, 4.92. Found: C, 39.82; H, 4.28; N, 4.90.
24. 2: C, 34.66; H, 3.51; N, 4.18. Found: C, 34.63; H, 3.15; N, 4.10.
25. 2Re: C, 33.99; H, 3.84; N, 4.10. Found: C, 33.71; H, 3.96; N, 4.11.
26. The ratio of isomers in isolated 5b is significantly different than the 5:2 ratio of its precursor. However, only 59% of the product is isolated from solution, and it is likely that one diasteromer is less soluble than the other.
27. 1H decoupling data.