Reactions of an imidozirconocene complex with cyclopentadienylmetal carbonyl complexes: C-H activation versus oxygen atom abstraction

Journal of the American Chemical Society

Volumn 117, Issue 21, 1995, Pages 5877-5878

  Lee, Sun Yeoul ^a   Bergman, Robert G ^a  

^a UNIVERSITY OF CALIFORNIA   (United States)

Author keywords

[No Author keywords available]

Indexed keywords

EID: 0000125617     PISSN: 00027863     EISSN: None     Source Type: Journal    
DOI: 10.1021/ja00126a038     Document Type: Article

References (26)

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7. 1H NMR) were generated during thermolysis at 75°C.
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14. 13C NMR spectrum.
15. Choukroun, R.; Raoult, Y.; Gervais, D. J. Organomet. Chem. 1990, 391, 189.
16. A referee has asked about the products formed on reaction of 2 with cyclopemadiene. Because of the ease of dimerization of this molecule, we have investigated the reactivity of 2 toward indene as an alternative. The final (presumably thermodynamic) product of this reaction (cyclohexane; 3 days at 75°C) is the benzylic indenyl(amido)zirconocene C-H activation product, whose structure has been determined by X-ray diffraction. Another indenyl(amido)zirconocene complex was detected as a kinetic product during the reaction. Spectroscopic data on this material indicate that it is the vinylic C-H activation product, but we have so far not been able to isolate it. We do not yet understand why attack at the five-memberedring hydrogens in indene appears to be favored over attack at the aryl hydrogens. This issue will be discussed, along with the details of the X-ray diffraction study, in a full paper.
17. 1H NMR) were generated. However, we were not able to isolate pure 8b from this mixture because of the very similar solubilities of this complex and the excess 7b still present in solution.
18. Beaumont, I.; Wright, A. H. J. Organomet. Chem. 1992. 425, C11.
19. Doherty, J.; Fortune, J.; Manning, A. R.; Stephens, F. S. J. Chem. Soc., Dalton Trans. 1984, 1111.
20. 6 demonstrates that THF is not required for the conversion of the starting terminal imido complex into an oxozirconium product.
21. 13C incorporation was determined by integration of relative mass peaks from EI mass spectroscopy.
22. Bergman, R. G.; Lee, S. Y. Unpublished results.
23. Proulx, G.; Bergman, R. G. J. Am. Chem. Soc. 1993, 115, 9802.
24. Housmekerides, C. E.; Ramage, D. L.; Kretz, C. M.; Shontz, J. T.; Pilato, R. S.; Geoffroy, G. L.; Rheingold, A. L.; Haggerty, B. S. Inorg. Chem. 1992, 31, 4453.
25. Pilato, R. S.; Rubin, D.; Geoffroy, G. L.; Rheingold, A. L. Inorg. Chem. 1990, 29, 1986.
26. 2Zr=O.