The lithiation of ferrocene and ruthenocene: A retraction and an improvement

Journal of Organometallic Chemistry

Volumn 512, Issue 1-2, 1996, Pages 219-224

  Sanders, Richard ^a   Mueller Westerhoff, Ulrich T ^a  

^a UNIVERSITY OF CONNECTICUT   (United States)

Author keywords

Aldehydes; Iron; Lithiation; Lithium; Metalations; Metallocenes; Ruthenium

Indexed keywords

EID: 0030593208     PISSN: 0022328X     EISSN: None     Source Type: Journal    
DOI: 10.1016/0022-328X(95)05914-B     Document Type: Article

References (9)

1. [1] U.T. Mueller-Westerhoff, Z. Yang and G. Ingram, J. Organomet. Chem., 463 (1993) 163.
2. [2] Professor H. Kagan, personal communication. We thank Professor Kagan for his help and analysis of the ferrocene lithiation problem.
3. [3] D. Guillaneux and H. Kagan, J. Org. Chem., 60 (1995) 2502.
4. [4] M.D. Rausch, E.O. Fischer and H. Grubert, J. Am. Chem. Soc., 82 (1960) 76.
5. [5] The early work has been reviewed: D.W. Slocum, T.R. Engelmann, C. Ernst, C.A. Jennings, B. Koonsvitsky, J. Lewis and P. Shenkin, J. Chem. Ed., 46 (1969) 144. There is little or no reaction in hexane; some lithiation occurs in diethyl ether. A mixture of mono-and dilithio-ferrocene is obtained in ether/THF: D. Mayo, P. Shaw and M.D. Rausch, Chem. Ind. (Lond.), (1957) 1388. Our own work has confirmed these observations.
6. [5] The early work has been reviewed: D.W. Slocum, T.R. Engelmann, C. Ernst, C.A. Jennings, B. Koonsvitsky, J. Lewis and P. Shenkin, J. Chem. Ed., 46 (1969) 144. There is little or no reaction in hexane; some lithiation occurs in diethyl ether. A mixture of mono-and dilithio-ferrocene is obtained in ether/THF: D. Mayo, P. Shaw and M.D. Rausch, Chem. Ind. (Lond.), (1957) 1388. Our own work has confirmed these observations.
7. [6] Because the GC integrals do not necessarily represent the true relative amounts, this assessment requires standardization, which was achieved by injecting GC-MS mixtures of components with known concentration and normalizing their integrals. This produced an analysis which agreed with the results from Chromatographic separation within 1%.
8. [7] L. Verbit and T.R. Haibert, Mol. Cryst Liq. Cryst., 30 (1975) 209.
9. [8] D.E. Bublitz, W.E. McEwen and J. Kleinberg, J. Am. Chem. Soc., 84 (1962) 1845.