Synthesis and metallation of ferrocenylimines derived from ligating diaminoheteroarenes

Abstract

A regioisomeric mixture of 1,1′-didodecylferrocenedicarbaldehydes 3 was prepared from the reaction of a regioisomeric mixture of 1,1′-didodecyldilithioferrocenes and dimethylformamide. Three ligating heteroaromatics were synthesized each containing two amino substituents: 5,5′-diamino-2,2′-bipyridine and 5,5″-diamino-2,2′∶6′,2″-terpyridine were prepared from appropriate dinitro compounds by reduction with palladium on charcoal–hydrazine hydrate. The reaction of 2-cyano-5-nitropyridine and hydrazine hydrate gave an isolable amidine derivative and this was transformed with hydrazine in a separate reaction under more forcing conditions into 3,6-bis(5-amino-2-pyridyl)-1,2-dihydro-1,2,4,5-tetrazine. The latter was converted into the tetrazine by oxidation (2,3-dichloro-5,6-dicyano-1,4-benzoquinone) and then trifluoroacetylated [(CF₃CO)₂O] to give the bis(trifluoroacetylamino) derivative. Diels–Alder reaction of the latter with dodec-1-yne afforded 4-n-decyl-3,6-bis[5-(trifluoroacetylamino)-2-pyridyl]pyridazine which was deprotected (K₂CO₃) to give the corresponding diamine. Bis(ferrocenyl) Schiff bases were prepared from ferrocenecarbaldehyde and the appropriate diamine in either uncatalysed or acid-catalysed condensations. Tetracarbonylmolybdenum complexes were prepared by treating the appropriate diamines with molybdenum hexacarbonyl. Reaction of one of these complexes with ferrocenecarbaldehyde gave a heterobimetallic complex.

References

1. See, for example, M. Sato, T. Hayashi, S. Kumakura, N. Shimizu, M. Katada and S. Kawata, Organometallics, 1996, 15, 721.
2. See, for example, M. J. Begley, P. Mountford, P. J. Stewart, D. Swallow and S. Wan, J. Chem. Soc., Dalton Trans., 1996, 1323.
3. See, for example, C. J. McAdam, N. W. Duffy, B. H. Robinson and J. Simpson, Organometallics, 1996, 15, 3935.
4. W. E. Lindsell, P. J. Tomb and P. N. Preston, J. Organomet. Chem., 1992, 439, 201.
5. N. M. Agh-Atabay, W. E. Lindsell, P. J. Tomb, P. N. Preston, A. D. Lloyd, R. Rangel-Rojo, G. Spruce and B. S. Wherrett, J. Mater. Chem., 1992, 2, 1241.
6. I. R. Butler, Organometallics, 1992, 11, 74.
7. I. R. Butler, D. S. Brassington, R. A. Bromley, P. Licence and J. Wrench, Polyhedron, 1996, 15, 4087.
8. E. C. Constable, A. J. Edwards, R. Martinez-Máñez, P. R. Raithby and A. M. W. Cargill-Thompson, J. Chem. Soc., Dalton Trans., 1995, 645.
9. E. C. Constable, A. J. Edwards, R. Martinez-Máñez and P. R. Raithby, J. Chem. Soc., Dalton Trans., 1995, 3253.
10. See, for example, R. Adams, R. E. Bullock and W. C. Wilson, J. Am. Chem. Soc., 1923, 45, 521; C. S. Marvel and P. V. Bonsignore, J. Am. Chem. Soc., 1959, 81, 2668.
11. See, for example, G. F. D'Alelio, W. F. Strazik, D. M. Feigl and R. K. Schoenig, J. Macromol. Sci. Chem., 1968, 2, 1457; G. F. D'Alelio, Encycl. Polym. Sci. Technol., 1969, 10, 659.
12. See, for example, S. Banerjee, P. K. Gutch and C. Saxena, J. Polym. Sci. A, 1995, 33, 1719; C. Mealares and A. Gandini, Polym. Int., 1996, 40, 33.
13. S. Park, H. Kim, W. Zin and J. C. Jung, Macromolecules, 1993, 26, 1627.
14. K. Sonogashira and N. Hagihari, Kogyo Kagaku Zasshi, 1963, 66, 1090.
15. E. W. Neuse, H. Rosenberg and R. R. Carten, Macromolecules, 1968, 1, 424.
16. M. Vogel, M. Rausch and H. Rosenberg, J. Org. Chem., 1957, 22, 1016.
17. See G. Tainturier and J. Tirouflet, Bull. Soc. Chim. Fr., 1966, 600.
18. See M. A. Carol, D. A. Widdowson and D. J. Williams, Synlett, 1994, 1025.
19. J. A. Connor and C. Overton, J. Organomet. Chem., 1983, 249, 165; J. A. Connor, C. Overton and N. El. Murr, J. Organomet. Chem., 1984, 277, 277.
20. F. Calogero, H. S. Freeman, J. F. Esancy, W. M. Whaley and B. J. Dabney, Dyes Pigm., 1987, 8, 431.
21. Y. Tohda, M. Eiraku, T. Nakagawa, Y. Usami, M. Ariga, T. Kawashima, K. Tani, H. Watanabe and Y. Mori, Bull. Chem. Soc. Jpn., 1990, 63, 2820.
22. D. L. Boger and S. M. Weinreb, Hetero Diels–Alder Methodology in Organic Synthesis, Academic Press, London, 1987, ch. 10.
23. J. F. Geldard and F. Lyons, J. Org. Chem., 1965, 30, 318.
24. See, for example, J. A. Deyrup and H. L. Gingrich, Tetrahedron Lett., 1977, 3115; T. Sasaki, K. Kanematsu and T. Kataoka, J. Org. Chem., 1975, 40, 1201; A. J. Ashe, D. J. Bellville and H. S. Friedman, J. Chem. Soc., Chem. Commun., 1979, 880.
25. P. J. Delaive, J. T. Lee, H. W. Sprintschnik, H. Albruna, T. J. Meyer and D. G. Whitten, J. Am. Chem. Soc., 1977, 99, 7094.
26. See M. H. B. Stiddard, J. Chem. Soc., 1962, 4712.
27. M. Ghedini, M. Longeri and F. Neve, J. Chem. Soc., Dalton Trans., 1986, 2669; M. Ghedini, F. Neve and M. C. Bruno, Inorg. Chim. Acta, 1988, 143, 89.