Synthesis of a ferrocene bridged cyclam: a new redox-active macrocycle and the structure of a nickel(II) complex with strongly coupled metal centers

Abstract

The reaction of 1,1′-ferrocene-bis(methylenepyridinium) with 1,4,8,11-tetraazacyclotetradecane-5,12-dione followed by reduction of the product with LiAlH₄ results in a ferrocene bridged cyclam, which is a very efficient redox-switch for transition metal ions due to the short iron-to-metal ion distances.

References

1. L. F. Lindoy, The Chemistry of Macrocyclic Ligand Complexes, Cambridge University Press, Melbourne, 1989.
2. M. Lachkar, R. Guilard, A. Atmani, A. deCian, J. Fischer and R. Weiss, Inorg. Chem., 1998, 37, 1575; M. R. Oberholzer, M. Neuburger, M. Zehnder and T. A. Kaden, Helv. Chim. Acta, 1995, 78, 505; J. R. Röper and H. Elias, Inorg. Chem., 1992, 31, 1202 and references therein.
3. E. Fujita, J. Haff, R. Sanzenbacher and H. Elias, Inorg. Chem., 1994, 33, 4627; G. Pozzi, M. Cavazzini, S. Quici and S. Fontana, Tetrahedron Lett., 1997, 38, 7605.
4. J. M. Lloris, R. Martínez-Máñez, T. Pardo, J. Soto and M. E. Padilla-Tosta, J. Chem. Soc., Dalton Trans., 1998, 2635.
5. P. D. Beer, Acc. Chem. Res., 1998, 31, 71.
6. A. M. Allgeier and C. A. Mirkin, Angew. Chem., 1998, 37, 937; Angew. Chem., Int. Ed., 1998, 37, 894.
7. H. Plenio and C. Aberle, Organometallics, 1997, 16, 5950.
8. H. Plenio and C. Aberle, Angew. Chem., 1998, 110, 1467; Angew. Chem., Int. Ed., 1998, 37, 1397.
9. F. Rabiet, F. Denat and R. Guilard, Synth. Commun., 1997, 27, 979.
10. M. J. L. Tendero, A. Benito, J. Cano, J. M. Lloris, R. Martínez-Máñez, J. Soto, A. J. Edwards, P. R. Raithby and M. A. Rennie, J. Chem. Soc., Chem. Commun., 1995, 1643.
11. G. DeSantis, L. Fabrizzi, M. Licchelli, C. Mangano, P. Pallavicini and A. Poggi, Inorg. Chem., 1993, 32, 854.
12. H. Plenio and D. Burth, Organometallics, 1996, 15, 4054.
13. B. Bosnich, C. K. Poon and M. L. Tobe, Inorg. Chem., 1965, 8, 1102.
14. H. Plenio and R. Diodone, J. Organomet. Chem., 1995, 492, 73 and references therein.
15. G. M. Sheldrick, SHELX—97, A Program Suite for the Solution and Refinement of Crystal Structures, University of Göttingen, 1997.