Skip to main content
SpringerLink
Log in

Developing a fulvene route to C1-bridged “constrained geometry” Ziegler catalyst systems

  • Published:
Topics in Catalysis Aims and scope Submit manuscript

Abstract

6-dimethylamino-6-methylfulvene (7) was converted to the [(C5H4)–CMe2–NMe2]− ligand system (8) by treatment with methyllithium. Its reaction with MCl4 (M = Zr, Ti) followed by treatment with CH3Li gave the respective [(C5H4)–CMe2–NMe2]2M(CH3)2 complexes (12). Their reaction with B(C6F5)3 led to reactive metallocene cation complexes that instantaneously underwent CH activation at a N–CH3 group to yield the metallacyclic cation complexes 15. (tert-butylaminomethyl)fluorene was prepared by the addition of tert-butylisocyanate to fluorenyllithium followed by hydride reduction. Deprotonation by a variety of bases gave rise to a series of competing and consecutive reactions to yield several unusually structured products, among them a fluorenyl-anellated η5-1-azapentadienyl anion equivalent (25) and [(flu)-CH2–NCMe3]Li2 (23). An improved way of generating synthetically useful C1-linked [Cp–C1(R) n –NR1]2- dianion equivalents was developed starting from 6-amino-6-methylfulvene (26). N-silylation followed by double deprotonation with, e.g., lithium diisopropylamide cleanly furnished the respective [(C5H4)–C(=CH2)–NSiMe3]2- dianion 33 (isolated as the dilithio derivative). Its reaction with Cl2Zr(NEt2)2 in THF gave [η5:κ-N-(C5H4)–C(=CH2)–NSiMe3]Zr(NEt2)2 36. Activation of 36 with methylalumoxane in toluene led to the formation of a C1-linked “constrained geometry” Ziegler catalyst that polymerized ethylene similarly as the [(C5Me4)SiMe2NCMe3]ZrCl2 derived literature system.

This is a preview of subscription content, log in via an institution to check access.

Access this article

Log in via an institution

Price excludes VAT (USA)
Tax calculation will be finalised during checkout.

Instant access to the full article PDF.

Institutional subscriptions

Similar content being viewed by others

References

  1. H. Sinn and W. Kaminsky, Adv. Organomet. Chem. 18 (1980) 99. R.F. Jordan, Adv. Organomet. Chem. 32 (1991) 325. T.J. Marks, Acc. Chem. Res. 25 (1992) 57. M. Aulbach and F. K¨uber, Chemie Unserer Zeit 28 (1994) 197. H.-H. Brintzinger, D. Fischer, R. M¨ulhaupt, B. Rieger and R. Waymouth, Angew. Chem. 107 (1995) 1255; Angew. Chem. Int. Ed. Engl. 34 (1995) 1143. M. Bochmann, J. Chem. Soc., Dalton Trans. (1996) 255 and references cited in these articles.

    Article  CAS  Google Scholar 

  2. C.K. Johnson, C.M. Killian and M. Brookhart, J. Am. Chem. Soc. 117 (1995) 6414. L.K. Johnson, S. Mecking and M. Brookhart, J. Am. Chem. Soc. 117 (1995) 11664. J.D. Scollard and D.H. McConville, J. Am. Chem. Soc. 118 (1996) 10008. G.C. Bazan, G. Rodriguez, A.J. Ashe III, S. Al-Ahmad and J.W. Kampf, Organometallics 16 (1997) 2492.

    Article  CAS  Google Scholar 

  3. P.J. Shapiro, W.D. Cotter, W.P. Schaefer, J.A. Labinger and J.E. Bercaw, J. Am. Chem. Soc. 116 (1994) 4623. W.E. Piers, P.J. Shapiro, E.E. Bunel and J.E. Bercaw, Synlett 2 (1990) 74. E.E. Bunel, B.J. Burger and J.E. Bercaw, J. Am. Chem. Soc. 110 (1988) 976. P.J. Shapiro, E.E. Bunel, W.P. Schaefer and J.E. Bercaw, Organometallics 9 (1990) 867.

    Article  CAS  Google Scholar 

  4. J.C. Stevens, F.J. Timmers, D.R. Wilson, G.F. Schmidt, P.N. Nickias, R.K. Rosen, G.W. Knight and S. Lai, Eur. Patent Appl. EP 416815-A2, 1991 (Dow Chemical Co.). J.M. Canich, Eur. Patent Appl. EP 420436-A1, 1991 (Exxon Chemical Co.). J.M. Canich, G.G. Hlatky and H.W. Turner, PCT Appl. WO 92–00333, 1992.

    Google Scholar 

  5. B. Rieger, J. Organomet. Chem. 420 (1991) C17. I.M. Ewen and P. Ahlberg, J. Am. Chem. Soc. 114 (1992) 10869. H.V.R. Dias, Z. Wang and S.G. Bott, J. Organomet. Chem. 508 (1996) 91. H.V.R. Dias and Z. Wang, J. Organomet. Chem. 539 (1997) 77. P.-J. Sinnema, L. van der Veen, A.L. Spek, N. Veldman and J.H. Teuben, Organometallics 16 (1997) 4245. P.T. Witte, A. Meetsma, B. Hessen and P.H.M. Budzelaar, J. Am. Chem. Soc. 119 (1997) 10561. L. Schwink, P. Knochel, T. Eberle and J. Okuda, Organometallics 17 (1998) 7.

    CAS  Google Scholar 

  6. K. Ziegler and W. Sch¨afer, Justus Liebigs Ann. Chem. 511 (1934) 101. K. Ziegler, H.-G. Gellert, H. Martin, K. Nagel and J. Schneider, Justus Liebigs Ann. Chem. 589 (1954) 91. M.F. Sullivan and W.F. Little, J. Organomet. Chem. 8 (1967) 277. P. Renaut, G. Tainturier and B. Gautheron, J. Organomet. Chem. 148 (1978) 35, 43. M.D. Brickhouse, R.R. Squires, J. Am. Chem. Soc. 110 (1988) 2706. J. Okuda, Chem. Ber. 122 (1989) 1075. T.J. Clark, C.M. Killian, S. Luthra and T.A. Nile, J. Organomet. Chem. 462 (1993) 247. R.R. Squires, Acc. Chem. Res. 25 (1992) 461.

    CAS  Google Scholar 

  7. K. Hafner, K.H. V¨opel, G. Ploss and C. K¨onig, Org. Synth. Coll. 5 (1973) 431. K. Hafner, G. Schultz and K. Wagner, Chem. Ber. 768 (1964) 539. K. Hafner, K.H. V¨opel, G. Ploss and C. K¨onig, Organic Synth. 47 (1967) 52 and references cited therein.

    Google Scholar 

  8. G. Erker, K. Berg, L. Treschanke and K. Engel, Inorg. Chem. 21 (1982) 1277.

    Article  CAS  Google Scholar 

  9. See for a comparison: P. Jutzi and T. Redeker, Eur. J. Inorg. Chem. 663 (1998) and references cited therein.

  10. For definitions of conformational metallocene descriptors and selected examples see: G. Erker, M. Aulbach, M. Knickmeier, D. Wingberm¨uhle, C. Kr¨uger, M. Nolte and S. Werner, J. Am. Chem. Soc. 115 (1993) 4590. R.M. Waymouth and G.W. Coates, Science 267 (1995) 222. E. Hauptmann, R.M. Waymouth and J.W. Ziller, J. Am. Chem. Soc. 117 (1995) 11586. M. Knickmeier, G. Erker and T. Fox, J. Am. Chem. Soc. 118 (1996) 9623.

    Article  CAS  Google Scholar 

  11. X. Yang, C.L. Stern and T.J. Marks, J. Am. Chem. Soc. 116 (1994) 10015.

    Article  CAS  Google Scholar 

  12. L. Jia, X. Yang, A. Ishihara and T.J. Marks, Organometallics 14 (1995) 3135. P.A. Deck and T.J. Marks, J. Am. Chem. Soc. 117 (1995) 6128.

    Article  CAS  Google Scholar 

  13. A. Bertuleit, C. Fritze, G. Erker and R. Fr¨ohlich, Organometallics 16 (1997) 2891.

    Article  CAS  Google Scholar 

  14. For other examples of water addition products to electrophilic titanocene complexes see, e.g.: U. Thewalt and B. Kebbel, J. Organomet. Chem. 150 (1978) 59. K. D¨oppert, J. Organomet. Chem. 178 (1979) C3. U. Thewalt and H.-P. Klein, J. Organomet. Chem. 194 (1980) 297. U. Thewalt and K. Berhalter, J. Organomet. Chem. 302 (1986) 193. U. Thewalt and B. Honold, J. Organomet. Chem. 348 (1988) 291.

    CAS  Google Scholar 

  15. A. Bertuleit, doctoral dissertation, Univ. M¨unster, 1998.

  16. M. Oberhoff, L. Duda, J. Karl, R. Mohr, G. Erker, R. Fr¨ohlich and M. Grehl, Organometallics 15 (1996) 4005.

    Article  CAS  Google Scholar 

  17. Y. Ito, T. Konoike and T. Saegusa, J. Organomet. Chem. 85 (1975) 395.

    Article  CAS  Google Scholar 

  18. R.R. Brooks, W. Rhine and G.D. Stucky, J. Am. Chem. Soc. 94 (1972) 7339. R.D. Culp and A.H. Cowley, Organometallics 15 (1996) 5380. M. Ha°kansson, C.-H. Ottosson, A. Boman and D. Johnels, Organometallics 17 (1998) 1208. See also: W.J. Evans, T.J. Boyle and J.W. Ziller, Organometallics 11 (1992) 3903.

    Article  CAS  Google Scholar 

  19. For leading references concerning 1-azapentadienyl anion chemistry see, e.g.: P.B. Hitchcock, M.F. Lappert and Z.-X. Wang, J. Chem. Soc., Chem. Commun. (1996) 1647. J.R. Bleeke, S.T. Luaders and K.D. Robinson, Organometallics 13 (1994) 1592. G. Boche, G. Fraenkel, J. Cabral, K. Harms, N.J.R.v.E. Hommes, J. Lohrenz, M. Marsch and P.v.R. Schleyer, J. Am. Chem. Soc. 114 (1992) 1562. G. Wolf and E.-U. W¨urthwein, Chem. Ber. 124 (1991) 889. M.-H. Cheng, C.-Y. Cheng, S.-L. Wang, S.-M. Peng and R.-S. Liu, Organometallics 9 (1990) 1853. H. Dietrich, W. Mahdi and R. Knorr, J. Am. Chem. Soc. 108 (1986) 2462.

  20. M. K¨onemann, G. Erker, R. Fr¨ohlich and E.-U. W¨urthwein, J. Am. Chem. Soc. 119 (1997) 11155.

    Article  Google Scholar 

  21. For a successful application of this route see, e.g.: M. K¨onemann, G. Erker, R. Fr¨ohlich and S. Kotila, Organometallics 16 (1997) 2900.

    Article  Google Scholar 

  22. R. Kempe, S. Brenner and P. Arndt, Z. Anorg. Allg. Chem. 621 (1995) 2021.

    Article  Google Scholar 

  23. L. Duda, G. Erker, R. Fr¨ohlich and F. Zippel, Eur. J. Inorg. Chem. (1998) 1153.

  24. G. Erker, S. Wilker, C. Kr¨uger and M. Nolte, Organometallics 12 (1993) 2140. G. Erker, S. Wilker, C. Kr¨uger and R. Goddard, J. Am. Chem. Soc. 114 (1992) 10983.

    Article  CAS  Google Scholar 

  25. See for a comparison: W.A. Herrmann, M.J.A. Morawietz and T. Priermeir, Angew. Chem. 106 (1994) 2025; Angew. Chem., Int. Ed. Engl. 33 (1994) 11946. U. B¨ohme and K.-H. Thiele, J. Organomet. Chem. 472 (1994) 39. J. Christoffers and R.G. Bergman, Angew. Chem. 107 (1995) 2423; Angew. Chem., Int. Ed. Engl. 34 (1995) 2266. G.A. Molander, H. Schumann, E.C.E. Rosenthal and J. Demtschuk, Organometallics 15 (1996) 3817. Y.-X. Chen, P.-F. Fu, C.L. Stern and T.J. Marks, Organometallics 16 (1997) 5958. B.E. Bosch, G. Erker, R. Fr¨ohlich and O. Meyer, Organometallics 16 (1997) 5449.

    CAS  Google Scholar 

  26. J. Okuda, F.J. Schattenmann, S. Wocaldo and W. Massa, Organometallics 14 (1995) 789. K.E. du Plooy, U. Rose, H.-C. Kang, J. Okuda and W. Massa, Chem. Ber. 129 (1996) 275. D.D. Devore, F.J. Timmers, D.L. Hasha, R.K. Rosen, T.J. Marks, P.A. Deck and C.L. Stern, Organometallics 14 (1995) 3132. Y.-X. Chen, C.L. Stern, S. Yang and T.J. Marks, J. Am. Chem. Soc. 118 (1996) 12451. T.K. Woo, P.M. Margl, J.C.W. Lohrenz, P.E. Blochl and T. Ziegler, J. Am. Chem. Soc. 118 (1996) 13021. W.A. Herrmann and M.J.A. Morawietz, J. Organomet. Chem. 482 (1994) 169. D.W. Carpinetti, L. Kloppenburg, J.T. Kupec and J.L. Petersen, Organometallics 15 (1996) 1572. L. Kloppenburg and J.L. Petersen, Organometallics 15 (1996) 7. A.L. McKnight, Md.A. Masood, R.M. Waymouth and D.A. Straus, Organometallics 16 (1997) 2879. Y.-X. Chen and T.J. Marks, Organometallics 16 (1997) 3649. F. Amor, T.P. Spaniol and J. Okuda, Organometallics 16 (1997) 4765 and references cited in these articles.

    Article  CAS  Google Scholar 

Download references

Author information

Authors and Affiliations

  1. Organisch-Chemisches Institut der Universität Münster, Corrensstrasse 40, D-48149, Münster, Germany

    Axel Bertuleit, Martin Könemann, Lothar Duda, Gerhard Erker & Roland Fröhlich

Authors
  1. Axel Bertuleit
    View author publications

    You can also search for this author in PubMed Google Scholar

  2. Martin Könemann
    View author publications

    You can also search for this author in PubMed Google Scholar

  3. Lothar Duda
    View author publications

    You can also search for this author in PubMed Google Scholar

  4. Gerhard Erker
    View author publications

    You can also search for this author in PubMed Google Scholar

  5. Roland Fröhlich
    View author publications

    You can also search for this author in PubMed Google Scholar

Rights and permissions

Reprints and permissions

About this article

Cite this article

Bertuleit, A., Könemann, M., Duda, L. et al. Developing a fulvene route to C1-bridged “constrained geometry” Ziegler catalyst systems. Topics in Catalysis 7, 37–44 (1999). https://doi.org/10.1023/A:1019172018940

Download citation

  • Issue Date:

  • DOI: https://doi.org/10.1023/A:1019172018940

Search

Navigation