Summary
New members of mixed metal termetallocenes, 1,1′-dirhodoceniumylferroceneII, and 1-cobaltoceniumyl,1′-rhodoceniumylferroceneIII, were prepared by statistical nucleophilic attack of dilithioferrocene on equimolar amounts of cobaltocenium and rhodocenium hexafluorophosphate. Subsequent hydride abstraction with tritylium hexafluorophosphate yielded the respective termetallocene dications. Also a new bimetallocene monocation, ferrocenylrhodoceniumI, a byproduct formed from partial protonation of dilithioferrocene, was identified. The new compounds were separated from undesired metallocenes, starting metallocenes, and byproducts by means of preparative HPLC. A reversed phase system was established which is sufficiently tuneable in selectivity to separate the different metallocene cationic species. The isolated compounds were characterized by NMR, IR, and ICP. through the delocalized system of π-electrons [2]. The realisation of threefold mixed metal termetallocenes allows direct comparison of the influence of different substituents on a bridging metallocene, which is of special interest for extreme push-pull aromatic compounds like neutral metallocenes substituted with valence trapped metallocene cations.
This is a preview of subscription content, log in via an institution to check access.
Similar content being viewed by others
References
A. Gieren, K. E., Schwarzhans, H. Schottenberger, C. Ruiz Perez, T. Hübner, X-ray Diffractional Structure Determination of the “Mixed Valence”-Bimetallocenylene Ferrocenylene-cobaltocenylenium hexafluorophosphate and its Charge Distribution. Conference Meeting of German-Austrian Chemists; Innsbruck, Austria (May 12–14, 1986) Abstract Bulletin, 78 (1986).
A. P. Kahn, D. A. Newman, K. P. C. Vollhardt, Synth. Lett.,3, 141 (1990).
R. Böse, R. L. Myrabo, D. A. Newman, K. P. C. Vollhardt, Angew. Chem.,102, 589 (1990).
E. W. Neuse, M. S. Loonat, Transition. Met. Chem.,6, 260 (1981).
K. E. Schwarzhans, H. Schottenberger, Z. Naturforsch.,38b, 1496 (1983).
K. P. C. Vollhardt, T. W. Weidman, Organometallics,3, 82 (1984).
P. Jutzi, J. Schnittger, Chem. Ber.,122, 629 (1989).
H. Lehmkuhl, H. F. Nehl, Chem. Ber.,117, 3343 (1984).
G. Ingram, P. Jaitner, K. E. Schwarzhans, Z. Naturforsch., 45b (1990).
X-ray crystal structure of 1,1′-dicobaltoceniumyl-ruthenocene,G. Ingram; unpublished.
K. E. Schwarzhans, W. Stolz, Monatsh. Chem.,118, 875 (1987).
C. Rieker, G. Ingram, P. Jaitner, H. Schottenberger, K. E. Schwarzhans, J. Organomet. Chem.,381, 127 (1990).
D. R. Baghurst, D. M. P. Mingos, M. J. Watson, J. Organomet. Chem.,368, C43–45 (1989).
E. O. Fischer, U. Zahn, Chemn. Ber.,92, 1624 (1959).
R. J. Angelici, E. O. Fischer, J. Am. Chem. Soc.,85, 8733 (1963).
I. R. Butler, W. R. Culen, J. Ni, S. J. Rettig, Organometallics,4, 2196 (1985).
M. D. Rausch, G. A. Moser, C. F. Meade, J. Organomet. Chem.,51, 1 (1973).
G. Brauer, Handbuch der Präp. Anorg. Chemie, Band 3, 1849, Enke, Stuttgart (1981).
N. ElMurr, J. Organomet. Chem.,208, C9 (1981).
Author information
Authors and Affiliations
Rights and permissions
About this article
Cite this article
Andre, M., Schottenberger, H., Tessadri, R. et al. Synthesis and preparative HPLC-separation of heteronuclear oligometallocenes. Isolation of cations of rhodocenylferrocene, 1,1′-dirhodocenylferrocene, and 1-cobaltocenyl-, 1′-rhodocenylferrocene. Chromatographia 30, 543–545 (1990). https://doi.org/10.1007/BF02269802
Received:
Accepted:
Issue Date:
DOI: https://doi.org/10.1007/BF02269802