Dendritic Carbosilanes Containing Silicon-Bonded 1-[C6H2(CH2NMe2) 2-3,5-Li-4] or 1-[C6H3(CH2NMe2)-4-Li-3] Mono- And Bis(amino)aryllithium End Groups: Structure of {[CH2SiMe2C6H3(CH 2NMe2)-4-Li-3]2}2

Organometallics

Volumn 18, Issue 2, 1999, Pages 268-276

  Kleij, Arjan W ^a   Kleijn, Henk ^a   Jastrzebski, Johann T B H ^a   Smeets, Wilberth J J ^b   Spek, Anthony L ^b   Van Koten, Gerard ^a  

^a UTRECHT UNIVERSITY   (Netherlands)

^b UTRECHT UNIVERSITY   (Netherlands)

Author keywords

[No Author keywords available]

Indexed keywords

EID: 0000179189     PISSN: 02767333     EISSN: None     Source Type: Journal    
DOI: 10.1021/om980627e     Document Type: Article

References (38)

1. For recent reviews on dendritic molecules see: (a) Newkome, G. R. Advances in Dendritic Macromolecules; JAI: Greenwich, CT, 1994; Vol. 1, 1995; Vol. 2. (b) Tomalia, D. A.; Durst, H. D. Topics in Current Chemistry; Weber, E., Ed.; Springer-Verlag: Berlin, 1993; Vol. 165, p 193. Issberner, J.; Moors, R.; Vögtl, F. Angew Chem., Int. Ed. Engl. 1994, 33, 2413. Frêchet, J. M. Science 1994, 263, 1710. (e) Tomalia, D. A. Adv. Mater. 1994, 6, 529.
2. For recent reviews on dendritic molecules see: (a) Newkome, G. R. Advances in Dendritic Macromolecules; JAI: Greenwich, CT, 1994; Vol. 1, 1995; Vol. 2. (b) Tomalia, D. A.; Durst, H. D. Topics in Current Chemistry; Weber, E., Ed.; Springer-Verlag: Berlin, 1993; Vol. 165, p 193. Issberner, J.; Moors, R.; Vögtl, F. Angew Chem., Int. Ed. Engl. 1994, 33, 2413. Frêchet, J. M. Science 1994, 263, 1710. (e) Tomalia, D. A. Adv. Mater. 1994, 6, 529.
3. For recent reviews on dendritic molecules see: (a) Newkome, G. R. Advances in Dendritic Macromolecules; JAI: Greenwich, CT, 1994; Vol. 1, 1995; Vol. 2. (b) Tomalia, D. A.; Durst, H. D. Topics in Current Chemistry; Weber, E., Ed.; Springer-Verlag: Berlin, 1993; Vol. 165, p 193. Issberner, J.; Moors, R.; Vögtl, F. Angew Chem., Int. Ed. Engl. 1994, 33, 2413. Frêchet, J. M. Science 1994, 263, 1710. (e) Tomalia, D. A. Adv. Mater. 1994, 6, 529.
4. For recent reviews on dendritic molecules see: (a) Newkome, G. R. Advances in Dendritic Macromolecules; JAI: Greenwich, CT, 1994; Vol. 1, 1995; Vol. 2. (b) Tomalia, D. A.; Durst, H. D. Topics in Current Chemistry; Weber, E., Ed.; Springer-Verlag: Berlin, 1993; Vol. 165, p 193. Issberner, J.; Moors, R.; Vögtl, F. Angew Chem., Int. Ed. Engl. 1994, 33, 2413. Frêchet, J. M. Science 1994, 263, 1710. (e) Tomalia, D. A. Adv. Mater. 1994, 6, 529.
5. For recent reviews on dendritic molecules see: (a) Newkome, G. R. Advances in Dendritic Macromolecules; JAI: Greenwich, CT, 1994; Vol. 1, 1995; Vol. 2. (b) Tomalia, D. A.; Durst, H. D. Topics in Current Chemistry; Weber, E., Ed.; Springer-Verlag: Berlin, 1993; Vol. 165, p 193. Issberner, J.; Moors, R.; Vögtl, F. Angew Chem., Int. Ed. Engl. 1994, 33, 2413. Frêchet, J. M. Science 1994, 263, 1710. (e) Tomalia, D. A. Adv. Mater. 1994, 6, 529.
6. (a) Cuadrado, I.; Morán, M.; Casado, C. M.; Alonso, B.; Lobete, F.; García, B.; Ibisate, M.; Losada, J. Organometallics 1996, 15, 5278.
7. (b) Lobete, F.; Cuadrado, I.; Casado, C. M.; Alonso, B.; Morán, M.; Losada, J. J. Organomet. Chem. 1996, 509, 109.
8. (c) Valério, C.; Fillaut, J. L.; Ruiz, J.; Guittard, J.; Biais, J. C.; Astruc, D. J. Am. Chem. Soc. 1997, 119, 2588.
9. (a) Miedaner, A.; Curtis, C. J.; Barkley, R. M.; Dubois, D. L. Inorg. Chem. 1994, 33.
10. (b) Bhyrappa, P.; Young, J. K.; Moore, J. S.; Suslick, K. S. J. Mol. Catal. 1996, 113, 109.
11. Knapen, J. W. J.; van der Made, A. W.; De Wilde, J. C.; van Leeuwen, P. W. M. N.; Wijkens, P.; Grove, D. M.; van Koten, G. Nature 1994, 372, 659.
12. (a) van Koten, G. Pure Appl. Chem. 1989, 61, 1681, and references cited therein.
13. (b) Rietveld, M. P. H.; Grove, D. M.; van Koten, G. New J. Chem. 1997, 21, 751.
14. (a) The first preliminary report of these polylithiated species was presented during the ACS polymer division meeting in Chicago, August 5, 1996.
15. (b) Jastrzebski, J. T. B. H.; van Koten, G.; Konijn, M.; Stam, C. H. J. Am. Chem. Soc. 1982, 104, 5490.
16. (c) Others have also reported the synthesis of lithiated carbosilanes. The main difference, however, is that these materials are less suitable for the introduction of metal sites on the periphery of the carbosilane backbone compared to the polylithiated carbosilane species presented in this paper. See: Vasilenko, N. G.; Getmanova, E. V.; Miakushev, V. D.; Rebrov, E. A.; Möller, M.; Muzafarov, A. M. Polym. Sci. 1997, 39, 9. Vasilenko, N. G.; Rebrove, E. A.; Muzafarov, A. M.; Esswein, B.; Striegel, B.; Möller, M. Macromol. Chem. Phys. 1998, 199, 889.
17. (c) Others have also reported the synthesis of lithiated carbosilanes. The main difference, however, is that these materials are less suitable for the introduction of metal sites on the periphery of the carbosilane backbone compared to the polylithiated carbosilane species presented in this paper. See: Vasilenko, N. G.; Getmanova, E. V.; Miakushev, V. D.; Rebrov, E. A.; Möller, M.; Muzafarov, A. M. Polym. Sci. 1997, 39, 9. Vasilenko, N. G.; Rebrove, E. A.; Muzafarov, A. M.; Esswein, B.; Striegel, B.; Möller, M. Macromol. Chem. Phys. 1998, 199, 889.
18. Steenwinkel, P.; James, S. L.; Grove, D. M.; Veldman, N.; Spek, A. L.; van Koten, G. Chem. Eur. J. 1996, 2, 1440.
19. 9d,e analogues of NCN.
20. See for instance: (a) Dani, P.; Karlen, T.; Gossage R. A.; Smeets, W. J. J.; Spek, A. L.; van Koten, G. J. Am. Chem. Soc. 1997, 119, 11317. (b) Liou, S.-Y.; Gozin, M.; Milstein, D. J. Chem. Soc., Chem. Commun. 1995, 1965; J. Am. Chem. Soc. 1995, 117, 9774. Gupta, M.; Hagen, C.; Kaska, W. C.; Cramer, R. E.; Jensen, C. G. J. Am. Chem. Soc. 1997, 119, 840. Steenwinkel, P.; Dijkstra, H. P.; Grove, D. M.; Lutz, M.; Spek, A. L.; van Koten, G. To be published. (e) Loeb, S. J.; Shimizu, G. K. H. J. Chem. Soc., Chem. Commun. 1993, 1395.
21. See for instance: (a) Dani, P.; Karlen, T.; Gossage R. A.; Smeets, W. J. J.; Spek, A. L.; van Koten, G. J. Am. Chem. Soc. 1997, 119, 11317. (b) Liou, S.-Y.; Gozin, M.; Milstein, D. J. Chem. Soc., Chem. Commun. 1995, 1965; J. Am. Chem. Soc. 1995, 117, 9774. Gupta, M.; Hagen, C.; Kaska, W. C.; Cramer, R. E.; Jensen, C. G. J. Am. Chem. Soc. 1997, 119, 840. Steenwinkel, P.; Dijkstra, H. P.; Grove, D. M.; Lutz, M.; Spek, A. L.; van Koten, G. To be published. (e) Loeb, S. J.; Shimizu, G. K. H. J. Chem. Soc., Chem. Commun. 1993, 1395.
22. See for instance: (a) Dani, P.; Karlen, T.; Gossage R. A.; Smeets, W. J. J.; Spek, A. L.; van Koten, G. J. Am. Chem. Soc. 1997, 119, 11317. (b) Liou, S.-Y.; Gozin, M.; Milstein, D. J. Chem. Soc., Chem. Commun. 1995, 1965; J. Am. Chem. Soc. 1995, 117, 9774. Gupta, M.; Hagen, C.; Kaska, W. C.; Cramer, R. E.; Jensen, C. G. J. Am. Chem. Soc. 1997, 119, 840. Steenwinkel, P.; Dijkstra, H. P.; Grove, D. M.; Lutz, M.; Spek, A. L.; van Koten, G. To be published. (e) Loeb, S. J.; Shimizu, G. K. H. J. Chem. Soc., Chem. Commun. 1993, 1395.
23. See for instance: (a) Dani, P.; Karlen, T.; Gossage R. A.; Smeets, W. J. J.; Spek, A. L.; van Koten, G. J. Am. Chem. Soc. 1997, 119, 11317. (b) Liou, S.-Y.; Gozin, M.; Milstein, D. J. Chem. Soc., Chem. Commun. 1995, 1965; J. Am. Chem. Soc. 1995, 117, 9774. Gupta, M.; Hagen, C.; Kaska, W. C.; Cramer, R. E.; Jensen, C. G. J. Am. Chem. Soc. 1997, 119, 840. Steenwinkel, P.; Dijkstra, H. P.; Grove, D. M.; Lutz, M.; Spek, A. L.; van Koten, G. To be published. (e) Loeb, S. J.; Shimizu, G. K. H. J. Chem. Soc., Chem. Commun. 1993, 1395.
24. See for instance: (a) Dani, P.; Karlen, T.; Gossage R. A.; Smeets, W. J. J.; Spek, A. L.; van Koten, G. J. Am. Chem. Soc. 1997, 119, 11317. (b) Liou, S.-Y.; Gozin, M.; Milstein, D. J. Chem. Soc., Chem. Commun. 1995, 1965; J. Am. Chem. Soc. 1995, 117, 9774. Gupta, M.; Hagen, C.; Kaska, W. C.; Cramer, R. E.; Jensen, C. G. J. Am. Chem. Soc. 1997, 119, 840. Steenwinkel, P.; Dijkstra, H. P.; Grove, D. M.; Lutz, M.; Spek, A. L.; van Koten, G. To be published. (e) Loeb, S. J.; Shimizu, G. K. H. J. Chem. Soc., Chem. Commun. 1993, 1395.
25. See for instance: (a) Dani, P.; Karlen, T.; Gossage R. A.; Smeets, W. J. J.; Spek, A. L.; van Koten, G. J. Am. Chem. Soc. 1997, 119, 11317. (b) Liou, S.-Y.; Gozin, M.; Milstein, D. J. Chem. Soc., Chem. Commun. 1995, 1965; J. Am. Chem. Soc. 1995, 117, 9774. Gupta, M.; Hagen, C.; Kaska, W. C.; Cramer, R. E.; Jensen, C. G. J. Am. Chem. Soc. 1997, 119, 840. Steenwinkel, P.; Dijkstra, H. P.; Grove, D. M.; Lutz, M.; Spek, A. L.; van Koten, G. To be published. (e) Loeb, S. J.; Shimizu, G. K. H. J. Chem. Soc., Chem. Commun. 1993, 1395.
26. 2. See: Steenwinkel, P.; James, S. L.; Grove, D. M.; Kooijman, H.; Spek, A. L.; van Koten, G. Organometallics 1997, 16, 513.
27. (a) van der Made, A. W.; van Leeuwen, P. W. M. N.; De Wilde, J. C.; Brandes, A. C. Adv. Mater. 1993, 5, (6), 466.
28. (b) van der Made, A. W.; van Leeuwen, P. W. M. N. J. Chem. Soc., Chem. Commun. 1992, 1400.
29. 4). See: (a) Weiss, E. Angew. Chem., Int. Ed. Engl. 1993, 32, 1501. (b) Wijkens, P.; van Koten, E. M.; Janssen, M. D.; Jastrzebski, J. T. B. H.; Spek, A. L.; van Koten, G. Angew. Chem., Int. Ed. Engl. 1995, 34, 219.
30. 4). See: (a) Weiss, E. Angew. Chem., Int. Ed. Engl. 1993, 32, 1501. (b) Wijkens, P.; van Koten, E. M.; Janssen, M. D.; Jastrzebski, J. T. B. H.; Spek, A. L.; van Koten, G. Angew. Chem., Int. Ed. Engl. 1995, 34, 219.
31. 6b except for the ones mentioned in the text.
32. Klumpp, G. W.; Geurink, P. J. A.; van Eikema Hommes, N. J. R.; De Kanter, F. J. J.; Vos, M. Recl. Trav. Chim. Pays-Bays 1986, 105, 398.
33. (a) van der Zeijden, A. A. H.; van Koten, G. Recl. Trav. Chim. Pays-Bas 1988, 107, 431.
34. (b) Schlengermann, R.; Sieler, J.; Jelonek, S.; Hey-Hawkins, E. Chem. Commun. 1997, 197.
35. Sheldrick, G. M. SHELXL93, Program for crystal structure refinement; University of Göttingen, Göttingen, Germany, 1993.
36. Sheldrick, G. M. SHELXS86, Program for crystal structure refinement; University of Göttingen, Göttingen, Germany, 1986.
37. Spek, A. L. Acta Crystallogr. 1990, A46, C-34.
38. 2-NCN-Li, some hydrolysis takes place prior to the transmetalation reaction. This is clearly shown by NMR spectroscopy, in which resonances are found which are attributed to nonmetalated NCN sites. By means of signal integration, the percentage of metalation could be calculated (95%). This incomplete metalation was confirmed by both elemental analyses and FAB mass spectrometry (see Experimental Section).