Synthesis of 2,6-diarylphenyldimethylsilyl cations: Polar-π distribution of cation character

Angewandte Chemie - International Edition

Volumn 47, Issue 9, 2008, Pages 1719-1722

  Duttwyler, Simon ^a   Do, Quyen Quyen ^a   Linden, Anthony ^a   Baldridge, Kim K ^a   Siegel, Jay S ^a  

^a UNIVERSITY OF ZURICH   (Switzerland)

Author keywords

Aromatic chemistry; Lewis acids; Polar effects; Silicon cations; Stereochemistry

Indexed keywords

POSITIVE IONS; SILICON;

AROMATIC CHEMISTRY; LEWIS ACIDS; SILICON CATIONS; STEREOCHEMISTRY;

ACIDS;

EID: 53549091860     PISSN: 14337851     EISSN: None     Source Type: Journal    
DOI: 10.1002/anie.200705291     Document Type: Article

References (46)

1. For original reports, see: a) J. B. Lambert, S. Zhang, C. L. Stern, J. C. Huffman, Science 1993, 260, 1917;
2. b) J. B. Lambert, S. Zhang, S. M. Ciro, Organometallics 1994, 13, 2430;
3. c) C. A. Reed, Z. Xie, R. Bau, A. Benesi, Science 1993, 262, 402.
4. For commentary, see: a) G. A. Olah, G. Rasul, X. Li, H. A. Buchholz, G. Sandford, G. K. S. Prakash, Science 1994, 263, 983;
5. b) L. Pauling, Science 1994, 263, 983;
6. c) J. B. Lambert, S. Zhang, Science 1994, 263, 984;
7. d) C. A. Reed, Z. Xie, Science 1994, 263, 985.
8. a) J. B. Lambert, Y. Zhao, Angew. Chem. 1997, 109, 389;
9. Angew. Chem. Int. Ed. Engl. 1997, 36, 400;
10. b) K.-C. Kim, C. A. Reed, D. W. Elliot, L. J. Mueller, F. Tham, L. Lin, J. B. Lambert, Science 2002, 297, 825.
11. a) T. Müller, Organosilicon Chemistry V (Eds.: N. Auner, J. Weis), Wiley-VCH, Weinheim, 2003, p. 34;
12. b) R. Meyer, K. Werner, T. Müller, Chem. Eur. J. 2002, 8, 1163;
13. c) R. Panisch, M. Bolte, T. Müller, Organometallics 2007, 26, 3524.
14. For isosteric neutral boron cognates, see: R. S. Simons, S. T. Haubrich, B. V. Mork, M. Niemeyer, P. P. Power, Main Group Chem. 1998, 2, 275.
15. For other main-group cations similarly stabilized, see: a) G. W. Rabe, N. W. Mitzel, Inorg. Chim. Acta 2001, 316, 132;
16. b) R. J. Wehmschulte, J. M. Steele, J. D. Young, M. A. Khan, J. Am. Chem. Soc. 2003, 125, 1470;
17. c) T. Müller, C. Bauch, M. Ostermeier, M. Bolte, N. Auner, J. Am. Chem. Soc. 2003, 125, 2158;
18. d) J. D. Young, M. A. Khan, R. J. Wehmschulte, Organometallics 2004, 23, 1965.
19. For general Group 14 reactive intermediate chemistry, see: a) V. Y. Lee, A. Sekiguchi, Acc. Chem. Res. 2007, 40, 410;
20. b) M. Igarashi, M. Ichinohe, A. Sekiguchi, J. Am Chem. Soc. 2007, 129, 12660;
21. c) M. Ichinohe, M. Igarashi, K. Sanuki, A. Sekiguchi, J. Am Chem. Soc. 2005, 127, 9978;
22. d) A. Sekiguchi, T. Matsuno, M. Ichinohe, J. Am Chem. Soc. 2000, 122, 11250.
23. For Hammett relations on polar-π effects, see: a) C.-T. Chen, J. S. Siegel, J. Am. Chem. Soc. 1994, 116, 5959;
24. b) F. Cozzi, J. S. Siegel, Pure Appl. Chem. 1995, 67, 683.
25. C.-J. Du, H. Hart, K. D. Ng, J. Org. Chem. 1986, 51, 3162.
26. Compounds 2a-d are inert in air for months. Compounds 2b-d were purified by recrystallization.
27. [11n]: a) Gaussian 98 (Revision A.7), M. J. Frisch, G. W. Trucks, H. B. Schlegel, G. E. Scuseria, M. A. Robb, J. R. Cheeseman, V. G. Zakrzewski, J. A. Montgomery, R. E. Stratmann, J. C. Burant, S. Dapprich, J. M. Millam, A. D. Daniels, K. N. Kudin, M. C. Strain, O. Farkas, J. Tomasi, V. Barone, M. Cossi, R. Cammi, B. Mennucci, C. Pomelli, C. Adamo, S. Clifford, J. Ochterski, G. A. Petersson, P. Y. Ayala, Q. Cui, K. Morokuma, D. K. Malick, A. D. Rabuck, K. Raghavachari, J. B. Foresman, J. Cioslowski, J. V. Ortiz, B. B. Stefanov, G. Liu, A. Liashenko, P. Piskorz, I. Komaromi, R. Gomperts, R. L. Martin, D. J. Fox, T. Keith, M. A. Al-Laham, C. Y. Peng, A. Nanayakkara, C. Gonzalez, M. Challacombe, P. M. W. Gill, B. G. Johnson, W. Chen, M. W. Wong, J. L. Andres, M. Head-Gordon, E. S. Replogle, J. A. Pople, Gaussian, Inc., Pittsburgh, PA, 1998;
28. b) M. W. Schmidt, K. K. Baldridge, J. A. Boatz, S. T. Elbert, M. S. Gordon, J. H. Jensen, S. Koseki, N. Matsunaga, K. A. Nguyen, S. Su, T. L. Windus, S. T. Elbert, J. Comput. Chem. 1993, 14, 1347;
29. c) C. Moøller, M. S. Plesset, Phys. Rev. 1934, 46, 618;
30. d) A. D. Becke, J. Chem. Phys. 1993, 98, 5648;
31. e) C. Lee, W. Yang, R. G. Parr, Phys. Rev. B 1988, 37, 785;
32. f) B. Miehlich, A. Savin, H. Stoll, H. Preuss, Chem. Phys. Lett. 1989, 157, 200;
33. g) T. H. Dunning, J. Chem. Phys. 1989, 90, 1007;
34. h) T. Koopmans, Physica 1934, 1, 104;
35. i) J. Almlof, B. Roos, U. Wahlgren, H. Johansen, J. Electron Spectrosc. Relat. Phenom. 1973, 2, 51;
36. j) K. D. Jordan, M. N. Paddon-Row, J. Phys. Chem. 1992, 96, 1188;
37. k) R. Ditchfield, J. Chem. Phys. 1972, 56, 5688;
38. l) K. Wolinski, J. F. Hinton, P. Pulay, J. Am. Chem. Soc. 1990, 112, 8251;
39. m) 3D-PLTORB: San Diego, 3D version: 1997;
40. n) K. K. Baldridge, J. P. Greenberg, J. Mol. Graphics 1995, 13, 63.
41. s conformer.
42. a) W. von E. Doering, M. Saunders, Tetrahedron 1958, 4, 178;
43. b) V. Koptyug, A. Rezvukhin, E. Lippmaa, R. Pehk, Tetrahedron Lett. 1968, 9, 4009-4012
44. ; c) C. A. Reed, N. L. P. Fackler, K.-C. Kim, D. Stasko, D. R. Evans, J. Am. Chem. Soc. 1999, 121, 6314.
45. S. M. Hubig, J. K. Kochi, J. Org. Chem. 2000, 65, 6807.
46. The shifts were not unambiguously characterized and no peaks in the region of greater than δ = 140 ppm were found.