Synthesis and characterization of the dilithium salt of the octasilyl[4]radialene dianion: Evidence for a lithium walk on the eight-center, ten-electron π-electron system

Angewandte Chemie - International Edition

Volumn 37, Issue 12, 1998, Pages 1661-1664

  Sekiguchi, Akira ^a   Matsuo, Tsukasa ^a   Sakurai, Hideki ^b  

^a UNIVERSITY OF TSUKUBA   (Japan)

^b TOKYO UNIVERSITY OF SCIENCE   (Japan)

Author keywords

Carbanions; Ion pairs; Lithium; Silicon; Solid state structures

Indexed keywords

EID: 0032479474     PISSN: 14337851     EISSN: None     Source Type: Journal    
DOI: 10.1002/(sici)1521-3773(19980703)37:12<1661::aid-anie1661>3.0.co;2-o     Document Type: Article

References (21)

1. For reviews see: a) K. Müllen, Chem. Rev. 1984, 84, 603; b) W. N. Setzer, P. von R. Schleyer, Adv. Organomet. Chem. 1985, 24, 353; C. Schade, P. von R. Schleyer, Adv. Organomet. Chem. 1987, 27, 169; M. Rabinovitz, Top. Curr. Chem. 1988, 14, 99; e) A. B. Sannigrahi, T. Kar, B. G. Niyogi, P. Hobza, P. von R. Schleyer, Chem. Rev. 1990, 90, 1061; f) H. Bock, K. Ruppert, C. Näther, Z. Havlas, H. F. Herrmann, C. Arad, I. Göbel, A. John, J. Meuret, S. Nick, A. Rauschenbach, W. Seitz, T. Vaupel, B. Solouki, Angew. Chem. 1992, 104, 564; Angew. Chem. Int. Ed. Engl. 1992, 31, 550; g) A.-M. Sapse, P. von R. Schleyer, Lithium Chemistry: A Theoretical and Experimental Overview, Wiley, New York, 1995.
2. For reviews see: a) K. Müllen, Chem. Rev. 1984, 84, 603; b) W. N. Setzer, P. von R. Schleyer, Adv. Organomet. Chem. 1985, 24, 353; C. Schade, P. von R. Schleyer, Adv. Organomet. Chem. 1987, 27, 169; M. Rabinovitz, Top. Curr. Chem. 1988, 14, 99; e) A. B. Sannigrahi, T. Kar, B. G. Niyogi, P. Hobza, P. von R. Schleyer, Chem. Rev. 1990, 90, 1061; f) H. Bock, K. Ruppert, C. Näther, Z. Havlas, H. F. Herrmann, C. Arad, I. Göbel, A. John, J. Meuret, S. Nick, A. Rauschenbach, W. Seitz, T. Vaupel, B. Solouki, Angew. Chem. 1992, 104, 564; Angew. Chem. Int. Ed. Engl. 1992, 31, 550; g) A.-M. Sapse, P. von R. Schleyer, Lithium Chemistry: A Theoretical and Experimental Overview, Wiley, New York, 1995.
3. For reviews see: a) K. Müllen, Chem. Rev. 1984, 84, 603; b) W. N. Setzer, P. von R. Schleyer, Adv. Organomet. Chem. 1985, 24, 353; c) C. Schade, P. von R. Schleyer, Adv. Organomet. Chem. 1987, 27, 169; M. Rabinovitz, Top. Curr. Chem. 1988, 14, 99; e) A. B. Sannigrahi, T. Kar, B. G. Niyogi, P. Hobza, P. von R. Schleyer, Chem. Rev. 1990, 90, 1061; f) H. Bock, K. Ruppert, C. Näther, Z. Havlas, H. F. Herrmann, C. Arad, I. Göbel, A. John, J. Meuret, S. Nick, A. Rauschenbach, W. Seitz, T. Vaupel, B. Solouki, Angew. Chem. 1992, 104, 564; Angew. Chem. Int. Ed. Engl. 1992, 31, 550; g) A.-M. Sapse, P. von R. Schleyer, Lithium Chemistry: A Theoretical and Experimental Overview, Wiley, New York, 1995.
4. For reviews see: a) K. Müllen, Chem. Rev. 1984, 84, 603; b) W. N. Setzer, P. von R. Schleyer, Adv. Organomet. Chem. 1985, 24, 353; C. Schade, P. von R. Schleyer, Adv. Organomet. Chem. 1987, 27, 169; d) M. Rabinovitz, Top. Curr. Chem. 1988, 14, 99; e) A. B. Sannigrahi, T. Kar, B. G. Niyogi, P. Hobza, P. von R. Schleyer, Chem. Rev. 1990, 90, 1061; f) H. Bock, K. Ruppert, C. Näther, Z. Havlas, H. F. Herrmann, C. Arad, I. Göbel, A. John, J. Meuret, S. Nick, A. Rauschenbach, W. Seitz, T. Vaupel, B. Solouki, Angew. Chem. 1992, 104, 564; Angew. Chem. Int. Ed. Engl. 1992, 31, 550; g) A.-M. Sapse, P. von R. Schleyer, Lithium Chemistry: A Theoretical and Experimental Overview, Wiley, New York, 1995.
5. For reviews see: a) K. Müllen, Chem. Rev. 1984, 84, 603; b) W. N. Setzer, P. von R. Schleyer, Adv. Organomet. Chem. 1985, 24, 353; C. Schade, P. von R. Schleyer, Adv. Organomet. Chem. 1987, 27, 169; M. Rabinovitz, Top. Curr. Chem. 1988, 14, 99; e) A. B. Sannigrahi, T. Kar, B. G. Niyogi, P. Hobza, P. von R. Schleyer, Chem. Rev. 1990, 90, 1061; f) H. Bock, K. Ruppert, C. Näther, Z. Havlas, H. F. Herrmann, C. Arad, I. Göbel, A. John, J. Meuret, S. Nick, A. Rauschenbach, W. Seitz, T. Vaupel, B. Solouki, Angew. Chem. 1992, 104, 564; Angew. Chem. Int. Ed. Engl. 1992, 31, 550; g) A.-M. Sapse, P. von R. Schleyer, Lithium Chemistry: A Theoretical and Experimental Overview, Wiley, New York, 1995.
6. For reviews see: a) K. Müllen, Chem. Rev. 1984, 84, 603; b) W. N. Setzer, P. von R. Schleyer, Adv. Organomet. Chem. 1985, 24, 353; C. Schade, P. von R. Schleyer, Adv. Organomet. Chem. 1987, 27, 169; M. Rabinovitz, Top. Curr. Chem. 1988, 14, 99; e) A. B. Sannigrahi, T. Kar, B. G. Niyogi, P. Hobza, P. von R. Schleyer, Chem. Rev. 1990, 90, 1061; f) H. Bock, K. Ruppert, C. Näther, Z. Havlas, H. F. Herrmann, C. Arad, I. Göbel, A. John, J. Meuret, S. Nick, A. Rauschenbach, W. Seitz, T. Vaupel, B. Solouki, Angew. Chem. 1992, 104, 564; Angew. Chem. Int. Ed. Engl. 1992, 31, 550; g) A.-M. Sapse, P. von R. Schleyer, Lithium Chemistry: A Theoretical and Experimental Overview, Wiley, New York, 1995.
7. For reviews see: a) K. Müllen, Chem. Rev. 1984, 84, 603; b) W. N. Setzer, P. von R. Schleyer, Adv. Organomet. Chem. 1985, 24, 353; C. Schade, P. von R. Schleyer, Adv. Organomet. Chem. 1987, 27, 169; M. Rabinovitz, Top. Curr. Chem. 1988, 14, 99; e) A. B. Sannigrahi, T. Kar, B. G. Niyogi, P. Hobza, P. von R. Schleyer, Chem. Rev. 1990, 90, 1061; f) H. Bock, K. Ruppert, C. Näther, Z. Havlas, H. F. Herrmann, C. Arad, I. Göbel, A. John, J. Meuret, S. Nick, A. Rauschenbach, W. Seitz, T. Vaupel, B. Solouki, Angew. Chem. 1992, 104, 564; Angew. Chem. Int. Ed. Engl. 1992, 31, 550; g) A.-M. Sapse, P. von R. Schleyer, Lithium Chemistry: A Theoretical and Experimental Overview, Wiley, New York, 1995.
8. For reviews see: a) K. Müllen, Chem. Rev. 1984, 84, 603; b) W. N. Setzer, P. von R. Schleyer, Adv. Organomet. Chem. 1985, 24, 353; C. Schade, P. von R. Schleyer, Adv. Organomet. Chem. 1987, 27, 169; M. Rabinovitz, Top. Curr. Chem. 1988, 14, 99; e) A. B. Sannigrahi, T. Kar, B. G. Niyogi, P. Hobza, P. von R. Schleyer, Chem. Rev. 1990, 90, 1061; f) H. Bock, K. Ruppert, C. Näther, Z. Havlas, H. F. Herrmann, C. Arad, I. Göbel, A. John, J. Meuret, S. Nick, A. Rauschenbach, W. Seitz, T. Vaupel, B. Solouki, Angew. Chem. 1992, 104, 564; Angew. Chem. Int. Ed. Engl. 1992, 31, 550; g) A.-M. Sapse, P. von R. Schleyer, Lithium Chemistry: A Theoretical and Experimental Overview, Wiley, New York, 1995.
9. For the recent works on the dynamics of carbanionic inversion, sec: a) H. J. Reich, K. J. Kulicke, J. Am. Chem. Soc. 1995, 117, 6621; b) R. W. Hoffmann, R. K. Dress, T. Ruhland, A. Wenzel, Chem. Ber. 1995, 128, 861; H. J. Reich, K. J. Kulicke, J. Am. Chem. Soc. 1996, 118, 273.
10. For the recent works on the dynamics of carbanionic inversion, sec: a) H. J. Reich, K. J. Kulicke, J. Am. Chem. Soc. 1995, 117, 6621; b) R. W. Hoffmann, R. K. Dress, T. Ruhland, A. Wenzel, Chem. Ber. 1995, 128, 861; H. J. Reich, K. J. Kulicke, J. Am. Chem. Soc. 1996, 118, 273.
11. For the recent works on the dynamics of carbanionic inversion, sec: a) H. J. Reich, K. J. Kulicke, J. Am. Chem. Soc. 1995, 117, 6621; b) R. W. Hoffmann, R. K. Dress, T. Ruhland, A. Wenzel, Chem. Ber. 1995, 128, 861; c) H. J. Reich, K. J. Kulicke, J. Am. Chem. Soc. 1996, 118, 273.
12. 3] (3 molar equiv) by irradiation (λ > 300 nm) under reflux in THF. However, when one molar equivalent of the manganese complex was used, the octasilyl-substituted trimethylenecyclopentene derivative was obtained in 17% yield. For π-electron systems, such as 1, derived from silicon-containing macrocyclic polyacetylene, see H. Sakurai, Pure Appl. Chem. 1996, 68, 327. For the trimethylenecyclopentene and its tetraanion tetralithium. see: A. Sekiguchi, T. Matsuo, C. Kabuto, Angew. Chem. 1997, 109, 2572; Angew. Chem. Int. Ed. Engl. 1997, 36, 2462.
13. 3] (3 molar equiv) by irradiation (λ > 300 nm) under reflux in THF. However, when one molar equivalent of the manganese complex was used, the octasilyl-substituted trimethylenecyclopentene derivative was obtained in 17% yield. For π-electron systems, such as 1, derived from silicon-containing macrocyclic polyacetylene, see H. Sakurai, Pure Appl. Chem. 1996, 68, 327. For the trimethylenecyclopentene and its tetraanion tetralithium. see: A. Sekiguchi, T. Matsuo, C. Kabuto, Angew. Chem. 1997, 109, 2572; Angew. Chem. Int. Ed. Engl. 1997, 36, 2462.
14. 3] (3 molar equiv) by irradiation (λ > 300 nm) under reflux in THF. However, when one molar equivalent of the manganese complex was used, the octasilyl-substituted trimethylenecyclopentene derivative was obtained in 17% yield. For π-electron systems, such as 1, derived from silicon-containing macrocyclic polyacetylene, see H. Sakurai, Pure Appl. Chem. 1996, 68, 327. For the trimethylenecyclopentene and its tetraanion tetralithium. see: A. Sekiguchi, T. Matsuo, C. Kabuto, Angew. Chem. 1997, 109, 2572; Angew. Chem. Int. Ed. Engl. 1997, 36, 2462.
15. 1]chloroform, TMS): δ= -7.8.
16. The [4]radialene dianion, which was obtained by metalating 1,2-dimethyl-3,4-bismethylenecyclobutene with nBuLi/KOtBu or nBuLi/ N,N,N′,N′-tetramethylethylenediamine, has been characterized by the quenching experiments, see: W. T. Thorstad, N. S. Mills, D. Q. Buckelew, L. S. Govea, J. Org. Chem. 1989, 54, 773.
17. o). Crystallographic data (excluding structure factors) for the structure reported in this paper have been deposited with the Cambridge Crystallographic Data Centre as supplementary publication no. CCDC-101 602. Copies of the data can be obtained free of charge on application to CCDC, 12 Union Road, Cambridge CB2 1EZ, UK (fax: (+44) 1223-336-033; e-mail: deposit@ccdc.cam.ac.uk).
18. 8]toluene. When the temperature is lowered, the crystals of the bis-contact ion pair precipitate which hampers the dynamic NMR study.
19. 8]THF, 298 K, LiCl in MeOH, external standard): δ = -0.38, -0.66.
20. + ion of the CIP remains unchanged because this ion is bound to the π-electron system of the framework.
21. 29Si NMR spectrum, four signals were observed at δ = - 15.7, - 14.3, - 12.6, and - 11.6.