Synthesis and reactions of metallo-diethynylbenzenes: building blocks for redox-active poly(phenyleneethynylene)s†

Abstract

The metallo-diethynylbenzene complex W([triple bond, length half m-dash]CC₆H₄C[triple bond, length half m-dash]CH-4)(dmpe)₂Cl, a precursor to metal-containing poly(phenyleneethynylene)s, has been prepared using alkyne-metathesis methodology and can be coupled into unsaturated organic frameworks at both the ethynyl moiety and the tungsten center and one-electron oxidized to the open-shell cation.

References

1. R. Giesa, J. Macromol. Sci., Rev. Macromol. Chem. Phys., 1996, C36, 631.
2. P. S. Weiss, L. A. Bumm, T. D. Dunbar, T. P. Burgin, J. M. Tour and D. L. Allara, in Molecular Electronics: Science and Technology, ed. A. Aviram and M. Ratner, New York Academy of Sciences, New York, 1998, p. 145.
3. J. S. Moore, Acc. Chem. Res., 1997, 30, 402; W. Holzer, A. Penzkofer, S.-H. Gong, A. P. Davey and W. J. Blau, Opt. Quantum. Electron., 1997, 29, 713; W. Zhao, H. Li, R. West and J. C. Wright, Chem. Phys. Lett., 1997, 281, 105.
4. T. M. Swager, Acc. Chem. Res., 1998, 31, 201.
5. (a) A. Mayr and S. Ahn, Adv. Transition Met. Coord. Chem., 1996, 1, 1; (b) H. Fischer, P. Hofmann, F. R. Kreissl, R. R. Schrock, U. Schubert and K. Weiss, Carbyne Complexes, VCH, Amsterdam, 1988; (c) M. A. Gallop and W. R. Roper, Adv. Organomet. Chem., 1986, 25, 121.
6. T. P. Pollagi, S. J. Geib and M. D. Hopkins, J. Am. Chem. Soc., 1994, 116, 6051; H. A. Brison, T. P. Pollagi, T. C. Stoner, S. J. Geib and M. D. Hopkins, Chem. Commun., 1997, 1263.
7. A. Harriman and R. Ziessel, Coord. Chem. Rev., 1998, 171, 331.
8. M. P. Y. Yu, K.-K. Cheung and A. Mayr, J. Chem. Soc., Dalton Trans., 1998, 2373.
9. J. S. Murdzek and R. R. Schrock in ref. 5(b), p. 147.
10. M. A. Stevenson and M. D. Hopkins, Organometallics, 1997, 16, 3572.
11. (a) E. O. Fischer, M. Schluge and J. O. Besenhard, Angew. Chem., Int. Ed. Engl., 1976, 15, 683; (b) D. E. Haines and M. D. Hopkins, in preparation.
12. M. H. Chisholm, B. W. Eichhorn, K. Folting, J. C. Huffman, C. D. Ontiveros, W. E. Streib and W. G. Van Der Sluys, Inorg. Chem., 1987, 26, 3183.
13. J. Manna, T. M. Gilbert, R. F. Dallinger, S. J. Geib and M. D. Hopkins, J. Am. Chem. Soc., 1992, 114, 5870.
14. A. B. Bocarsly, R. E. Cameron, H.-D. Rubin, G. A. McDermott, C. R. Wolff and A. Mayr, Inorg. Chem., 1985, 24, 3976.