Norbornyl cations of group 14 elements

Journal of the American Chemical Society

Volumn 125, Issue 8, 2003, Pages 2158-2168

  Müller, Thomas ^a   Bauch, Christian ^a   Ostermeier, Markus ^a   Bolte, Michael ^a   Auner, Norbert ^a  

^a GOETHE UNIVERSITY   (Germany)

Author keywords

[No Author keywords available]

Indexed keywords

ELECTROPHILICITY;

CHEMICAL BONDS; NUCLEAR MAGNETIC RESONANCE; ORGANIC COMPOUNDS; QUANTUM THEORY; SOLVENTS; SYNTHESIS (CHEMICAL); THERMODYNAMIC STABILITY;

POSITIVE IONS;

CATION; CYCLOPENTENE DERIVATIVE; LEAD; SILICON;

ADDITION REACTION; ARTICLE; CHEMICAL STRUCTURE; COVALENT BOND; MOLECULAR INTERACTION; NUCLEAR MAGNETIC RESONANCE; QUANTUM MECHANICS; ROOM TEMPERATURE;

EID: 0037467134     PISSN: 00027863     EISSN: None     Source Type: Journal    
DOI: 10.1021/ja021234g     Document Type: Article

References (139)

1. Review: Lenoir, D.; Siehl, H.-U.; Subramanian, L. R. In Houben-Weyl, Methoden der Organischen Chemie; Hanack, M., Ed.; Thieme Verlag: Stuttgart, Germany, 1990; Vol. 19c.
2. Persistent carbocations: (b) Olah, G. A. Angew. Chem. 1995, 107, 1519; Angew. Chem., Int. Ed. Engl. 1995, 34, 1393.
3. Persistent carbocations: (b) Olah, G. A. Angew. Chem. 1995, 107, 1519; Angew. Chem., Int. Ed. Engl. 1995, 34, 1393.
4. (c) Olah, G. A. J. Org. Chem. 2001, 66, 5944.
5. Reviews: (a) Maerker, C.; Schleyer, P. v. R. In The chemistry of organic silicon Compounds; Rappoport, Z., Apeloig, Y., Eds.; Wiley: Chichester, U.K., 1998; Vol. 2, p 513.
6. (b) Lickiss, P. D. In The chemistry of organic silicon compounds; Rappoport, Z., Apeloig, Y., Eds.; Wiley: Chichester, U.K., 1998; Vol. 2, p 557.
7. (c) Lambert, J. B.; Kania, L.; Zhang, S. Chem. Rev. 1995, 95, 1.
8. (d) Reed, C. A. Acc. Chem. Res. 1998, 31, 325.
9. (e) Fornarini, S. In The chemistry of organic silicon compounds; Rappoport, Z., Apeloig, Y., Eds.; Wiley: Chichester, U.K., 2001; Vol. 3. p 1027.
10. (a) Lambert, J. B.; Zhao, Y. Angew. Chem., Int. Ed. Engl. 1997, 36, 400.
11. (b) Lambert, J. B.; Zhao, Y.; Wu, H.; Tse, W. C.; Kuhlmann, B. J. Am. Chem. Soc. 1999, 121, 5001.
12. (c) Müller, T.; Zhao, Y.; Lambert, J. B. Organometallics 1998, 17, 278.
13. (d) Kraka, E.; Sosa, C. P.; Gräfenstein, J.; Cremer, D. Chem. Phys. Lett. 1997, 9 (279).
14. (e) Lambert, J. B.; Lin, L. J. Org. Chem. 2001, 66, 8537.
15. (f) Kim, K.-C.; Reed, C. A.; Elliott, D. W.; Mueller, L. J.; Tham, F.; Lin, L.; Lambert, J. B. Science 2002, 297, 825.
16. (a) Nishinaga, T.; Izukawa, Y.; Komatsu, K. J. Am. Chem. Soc. 2000, 122, 9312.
17. (b) Nishinaga, T.; Izukawa, Y.; Komatsu, K. Tetrahedron 2001, 57, 3645.
18. Sekiguchi, A.; Matsuno, T.; Ichinohe, M. J. Am. Chem. Soc. 2000, 122, 11250.
19. (a) Sekiguchi, A.; Tsukamoto, M.; Ichinohe, M. Science 1997, 275, 60.
20. (b) Sekiguchi, A.; Fukaya, N.; Ichinohe, M.; Ishida, Y. Eur. J. Inorg. Chem. 2000, 1155.
21. (a) Basch, H.; Hoz, T. In The chemistry of organic germanium, tin and lead compounds; Patai, S., Rappoport, Z., Eds.; Wiley: Chichester, U.K., 1995; p 1.
22. (b) Karni, M.; Kapp, J.; Schleyer, P. v. R.; Apeloig, Y. In The chemistry of organic silicon compounds; Rappoport, Z., Apeloig, Y., Eds.; Wiley: Chichester, U.K., 2001; Vol. 3, p 1.
23. (c) Zharov, I.; Michl, J. In The chemistry of organic germanium, tin and lead compounds; Rappoport, Z., Apeloig, Y., Eds.; Wiley: Chichester, U.K., 2002; Vol. 2, p 1.
24. For solvated cationic stannyl and plumbyl compounds see: (a) Kira, M.; Oyamada, T.; Sakurai, H. J. Organomet. Chem. 1994, 471, C4. (b) Lambert, J. B.; Kuhlmann, B. J. Chem. Soc., Chem. Commun. 1992, 931. (c) Edlund, U.; Arshadi, M.; Johnels, D. J. Organomet. Chem. 1993, 456, 57. (d) Arshadi, M.; Johnels, D.; Edlund, U. J. Chem. Soc., Chem. Commun. 1996, 1279. (e) Henderson, L. D.; Piers, W. E.; Irvine, G. J.; McDonald, R. Organometallics 2002, 21, 340. (f) Lambert, J. B.; Zhao, Y.; Wu, H. J. Org. Chem. 1999, 64, 2729.
25. For solvated cationic stannyl and plumbyl compounds see: (a) Kira, M.; Oyamada, T.; Sakurai, H. J. Organomet. Chem. 1994, 471, C4. (b) Lambert, J. B.; Kuhlmann, B. J. Chem. Soc., Chem. Commun. 1992, 931. (c) Edlund, U.; Arshadi, M.; Johnels, D. J. Organomet. Chem. 1993, 456, 57. (d) Arshadi, M.; Johnels, D.; Edlund, U. J. Chem. Soc., Chem. Commun. 1996, 1279. (e) Henderson, L. D.; Piers, W. E.; Irvine, G. J.; McDonald, R. Organometallics 2002, 21, 340. (f) Lambert, J. B.; Zhao, Y.; Wu, H. J. Org. Chem. 1999, 64, 2729.
26. For solvated cationic stannyl and plumbyl compounds see: (a) Kira, M.; Oyamada, T.; Sakurai, H. J. Organomet. Chem. 1994, 471, C4. (b) Lambert, J. B.; Kuhlmann, B. J. Chem. Soc., Chem. Commun. 1992, 931. (c) Edlund, U.; Arshadi, M.; Johnels, D. J. Organomet. Chem. 1993, 456, 57. (d) Arshadi, M.; Johnels, D.; Edlund, U. J. Chem. Soc., Chem. Commun. 1996, 1279. (e) Henderson, L. D.; Piers, W. E.; Irvine, G. J.; McDonald, R. Organometallics 2002, 21, 340. (f) Lambert, J. B.; Zhao, Y.; Wu, H. J. Org. Chem. 1999, 64, 2729.
27. For solvated cationic stannyl and plumbyl compounds see: (a) Kira, M.; Oyamada, T.; Sakurai, H. J. Organomet. Chem. 1994, 471, C4. (b) Lambert, J. B.; Kuhlmann, B. J. Chem. Soc., Chem. Commun. 1992, 931. (c) Edlund, U.; Arshadi, M.; Johnels, D. J. Organomet. Chem. 1993, 456, 57. (d) Arshadi, M.; Johnels, D.; Edlund, U. J. Chem. Soc., Chem. Commun. 1996, 1279. (e) Henderson, L. D.; Piers, W. E.; Irvine, G. J.; McDonald, R. Organometallics 2002, 21, 340. (f) Lambert, J. B.; Zhao, Y.; Wu, H. J. Org. Chem. 1999, 64, 2729.
28. For solvated cationic stannyl and plumbyl compounds see: (a) Kira, M.; Oyamada, T.; Sakurai, H. J. Organomet. Chem. 1994, 471, C4. (b) Lambert, J. B.; Kuhlmann, B. J. Chem. Soc., Chem. Commun. 1992, 931. (c) Edlund, U.; Arshadi, M.; Johnels, D. J. Organomet. Chem. 1993, 456, 57. (d) Arshadi, M.; Johnels, D.; Edlund, U. J. Chem. Soc., Chem. Commun. 1996, 1279. (e) Henderson, L. D.; Piers, W. E.; Irvine, G. J.; McDonald, R. Organometallics 2002, 21, 340. (f) Lambert, J. B.; Zhao, Y.; Wu, H. J. Org. Chem. 1999, 64, 2729.
29. For solvated cationic stannyl and plumbyl compounds see: (a) Kira, M.; Oyamada, T.; Sakurai, H. J. Organomet. Chem. 1994, 471, C4. (b) Lambert, J. B.; Kuhlmann, B. J. Chem. Soc., Chem. Commun. 1992, 931. (c) Edlund, U.; Arshadi, M.; Johnels, D. J. Organomet. Chem. 1993, 456, 57. (d) Arshadi, M.; Johnels, D.; Edlund, U. J. Chem. Soc., Chem. Commun. 1996, 1279. (e) Henderson, L. D.; Piers, W. E.; Irvine, G. J.; McDonald, R. Organometallics 2002, 21, 340. (f) Lambert, J. B.; Zhao, Y.; Wu, H. J. Org. Chem. 1999, 64, 2729.
30. Zharov, I.; King, B. T.; Havlas, Z.; Pardi, A.; Michi, J. J. Am. Chem. Soc. 2000, 122, 10253.
31. (a) Corey, J. Y. J. Am. Chem. Soc. 1975, 97, 3237.
32. (b) Mayr, H.; Basso, N. J. Am. Chem. Soc. 1992, 114, 3060.
33. (c) Apeloig, Y.; Merin-Aharoni, O.; Danovich, D.; Ioffe, A.; Shaik, S. Isr. J. Chem. 1993, 33, 387.
34. For examples of ammonium ions see: (a) Hensen, K.; Zengerley, T.; Pickel, P.; Klebe, G. Angew. Chem., Int. Ed. Engl. 1983, 22, 725. (b) Bassindale, A. R., Stout, Tetrahedron Lett. 1985, 26, 3403. (c) Hensen, K.; Zengerley, T.; Müller, T.; Pickel, P. Z. Anorg. Allg. Chem. 1988, 558, 21. (d) MacLachlan, M. J.; Bourke, S. C.; Lough, A. J.; Manners, I. J. Am. Chem. Soc. 2000, 122, 2126.
35. For examples of ammonium ions see: (a) Hensen, K.; Zengerley, T.; Pickel, P.; Klebe, G. Angew. Chem., Int. Ed. Engl. 1983, 22, 725. (b) Bassindale, A. R., Stout, Tetrahedron Lett. 1985, 26, 3403. (c) Hensen, K.; Zengerley, T.; Müller, T.; Pickel, P. Z. Anorg. Allg. Chem. 1988, 558, 21. (d) MacLachlan, M. J.; Bourke, S. C.; Lough, A. J.; Manners, I. J. Am. Chem. Soc. 2000, 122, 2126.
36. For examples of ammonium ions see: (a) Hensen, K.; Zengerley, T.; Pickel, P.; Klebe, G. Angew. Chem., Int. Ed. Engl. 1983, 22, 725. (b) Bassindale, A. R., Stout, Tetrahedron Lett. 1985, 26, 3403. (c) Hensen, K.; Zengerley, T.; Müller, T.; Pickel, P. Z. Anorg. Allg. Chem. 1988, 558, 21. (d) MacLachlan, M. J.; Bourke, S. C.; Lough, A. J.; Manners, I. J. Am. Chem. Soc. 2000, 122, 2126.
37. For examples of ammonium ions see: (a) Hensen, K.; Zengerley, T.; Pickel, P.; Klebe, G. Angew. Chem., Int. Ed. Engl. 1983, 22, 725. (b) Bassindale, A. R., Stout, Tetrahedron Lett. 1985, 26, 3403. (c) Hensen, K.; Zengerley, T.; Müller, T.; Pickel, P. Z. Anorg. Allg. Chem. 1988, 558, 21. (d) MacLachlan, M. J.; Bourke, S. C.; Lough, A. J.; Manners, I. J. Am. Chem. Soc. 2000, 122, 2126.
38. For examples of silylnitrilium ions see: (a) Olah, G. A.; Narang, S. C.; Gupta, B. G. B.; Malhotra, R. J. Org. Chem. 1979, 44, 1247. (b) Kira, M.; Hino, T.; Sakurai, H. Chem. Lett. 1993, 555. (c) Bahr, S. R.; Boudjouk, P. J. Am. Chem. Soc. 1993, 115, 4514. (d) Xie, Z.; Liston. D. J.; Jelinek, T.; Mitro, V.; Bau, R.; Reed, C. A. J. Chem. Soc., Chem. Commun. 1993, 384. (e) Lambert, J. B.; Zhang, S.; Ciro, S. M. Organometallics 1994, 13, 2430.
39. For examples of silylnitrilium ions see: (a) Olah, G. A.; Narang, S. C.; Gupta, B. G. B.; Malhotra, R. J. Org. Chem. 1979, 44, 1247. (b) Kira, M.; Hino, T.; Sakurai, H. Chem. Lett. 1993, 555. (c) Bahr, S. R.; Boudjouk, P. J. Am. Chem. Soc. 1993, 115, 4514. (d) Xie, Z.; Liston. D. J.; Jelinek, T.; Mitro, V.; Bau, R.; Reed, C. A. J. Chem. Soc., Chem. Commun. 1993, 384. (e) Lambert, J. B.; Zhang, S.; Ciro, S. M. Organometallics 1994, 13, 2430.
40. For examples of silylnitrilium ions see: (a) Olah, G. A.; Narang, S. C.; Gupta, B. G. B.; Malhotra, R. J. Org. Chem. 1979, 44, 1247. (b) Kira, M.; Hino, T.; Sakurai, H. Chem. Lett. 1993, 555. (c) Bahr, S. R.; Boudjouk, P. J. Am. Chem. Soc. 1993, 115, 4514. (d) Xie, Z.; Liston. D. J.; Jelinek, T.; Mitro, V.; Bau, R.; Reed, C. A. J. Chem. Soc., Chem. Commun. 1993, 384. (e) Lambert, J. B.; Zhang, S.; Ciro, S. M. Organometallics 1994, 13, 2430.
41. For examples of silylnitrilium ions see: (a) Olah, G. A.; Narang, S. C.; Gupta, B. G. B.; Malhotra, R. J. Org. Chem. 1979, 44, 1247. (b) Kira, M.; Hino, T.; Sakurai, H. Chem. Lett. 1993, 555. (c) Bahr, S. R.; Boudjouk, P. J. Am. Chem. Soc. 1993, 115, 4514. (d) Xie, Z.; Liston. D. J.; Jelinek, T.; Mitro, V.; Bau, R.; Reed, C. A. J. Chem. Soc., Chem. Commun. 1993, 384. (e) Lambert, J. B.; Zhang, S.; Ciro, S. M. Organometallics 1994, 13, 2430.
42. For examples of silylnitrilium ions see: (a) Olah, G. A.; Narang, S. C.; Gupta, B. G. B.; Malhotra, R. J. Org. Chem. 1979, 44, 1247. (b) Kira, M.; Hino, T.; Sakurai, H. Chem. Lett. 1993, 555. (c) Bahr, S. R.; Boudjouk, P. J. Am. Chem. Soc. 1993, 115, 4514. (d) Xie, Z.; Liston. D. J.; Jelinek, T.; Mitro, V.; Bau, R.; Reed, C. A. J. Chem. Soc., Chem. Commun. 1993, 384. (e) Lambert, J. B.; Zhang, S.; Ciro, S. M. Organometallics 1994, 13, 2430.
43. For examples of silylnitrilium ions see: (a) Olah, G. A.; Narang, S. C.; Gupta, B. G. B.; Malhotra, R. J. Org. Chem. 1979, 44, 1247. (b) Kira, M.; Hino, T.; Sakurai, H. Chem. Lett. 1993, 555. (c) Bahr, S. R.; Boudjouk, P. J. Am. Chem. Soc. 1993, 115, 4514. (d) Xie, Z.; Liston. D. J.; Jelinek, T.; Mitro, V.; Bau, R.; Reed, C. A. J. Chem. Soc., Chem. Commun. 1993, 384. (e) Lambert, J. B.; Zhang, S.; Ciro, S. M. Organometallics 1994, 13, 2430. (f) Johannsen, M.; Jorgensen, K. A.; Helmchen, G. J. Am. Chem. Soc. 1998, 120, 7637.
44. For examples of silyloxonium ions see: (a) Kira, M.; Hino, T.; Sakurai, H.; J. Am. Chem. Soc. 1992, 114, 6697. (b) Olah, G. A., Li, X.-Y., Wang, Q.; Rasul, G.; Prakash, G. K. S. J. Am. Chem. Soc. 1995, 117, 8962. (c) Xie, Z.; Bau, R.; Reed, C. A. J. Chem. Soc., Chem. Commun. 1994, 2519. (d) Driess, M.; Barmeyer, R.; Monsé, C.; Merz, K. Angew. Chem., Int. Ed. 2001, 40, 2308.
45. For examples of silyloxonium ions see: (a) Kira, M.; Hino, T.; Sakurai, H.; J. Am. Chem. Soc. 1992, 114, 6697. (b) Olah, G. A., Li, X.-Y., Wang, Q.; Rasul, G.; Prakash, G. K. S. J. Am. Chem. Soc. 1995, 117, 8962. (c) Xie, Z.; Bau, R.; Reed, C. A. J. Chem. Soc., Chem. Commun. 1994, 2519. (d) Driess, M.; Barmeyer, R.; Monsé, C.; Merz, K. Angew. Chem., Int. Ed. 2001, 40, 2308.
46. For examples of silyloxonium ions see: (a) Kira, M.; Hino, T.; Sakurai, H.; J. Am. Chem. Soc. 1992, 114, 6697. (b) Olah, G. A., Li, X.-Y., Wang, Q.; Rasul, G.; Prakash, G. K. S. J. Am. Chem. Soc. 1995, 117, 8962. (c) Xie, Z.; Bau, R.; Reed, C. A. J. Chem. Soc., Chem. Commun. 1994, 2519. (d) Driess, M.; Barmeyer, R.; Monsé, C.; Merz, K. Angew. Chem., Int. Ed. 2001, 40, 2308.
47. For examples of silyloxonium ions see: (a) Kira, M.; Hino, T.; Sakurai, H.; J. Am. Chem. Soc. 1992, 114, 6697. (b) Olah, G. A., Li, X.-Y., Wang, Q.; Rasul, G.; Prakash, G. K. S. J. Am. Chem. Soc. 1995, 117, 8962. (c) Xie, Z.; Bau, R.; Reed, C. A. J. Chem. Soc., Chem. Commun. 1994, 2519. (d) Driess, M.; Barmeyer, R.; Monsé, C.; Merz, K. Angew. Chem., Int. Ed. 2001, 40, 2308.
48. (a) Lambert, J. B.; Zhang, S.; Stem, C.; Huffman, J. C. Science 1993, 260, 1917.
49. (b) Lambert, J. B.; Zhang, S. J. Chem. Soc., Chem. Commun. 1993, 383.
50. (c) Lambert, J. B.; Zhang, S. Science 1994, 263, 984.
51. (d) Schleyer, P. v. R.; Buzek, P.; Müller, T.; Apeloig, Y.; Siehl, H.-U. Angew. Chem., Int. Ed. Engl. 1993, 32, 1471.
52. (e) Olsson, L.; Cremer, D. Chem. Phys. Lett. 1993, 6, 360.
53. (f) Arshadi, M.; Johnels, D.; Edlund, U.; Ottoson, C.-H. Cremer, D. J. Am. Chem. Soc. 1996, 118, 5120.
54. (g) Olah, G. A.; Rasul, G.; Buchholz, H. A.; Li, X.-Y.; Prakash, G. K. S. Bull. Soc. Chim. Fr. 1995, 132, 569.
55. (h) Olah, G. A.; Rasul, G.; Buchholz, H. A.; Li, X.-Y.; Sandford, G.: Prakash, G. K. S. Science 1994, 263, 983.
56. (i) Reed, C. A.; Xie, Z. Science 1994, 263, 985.
57. (j) Pauling, L. Science 1994, 263, 983.
58. (a) Chuit, C.; Corriu, R. J. P.; Mehdi, A.; Reyé, C. Angew. Chem., Int. Ed. Engl. 1993, 32, 1311.
59. (b) Belzner, J.; Schär, D.; Kneisel, B. O.; Herbst-Inner, R. Organometallics 1995, 14, 1840.
60. (c) Berlekamp, U.-H.; Jutzi, P.; Mix, A.; Neumann, B.; Stammler, H.-G.; Schoeller, W. W. Angew. Chem., Int. Ed. 1999, 38, 2048.
61. (d) Schmidt, H.; Keitemeyer, S.; Neumann, B.; Stammler, H.-G.; Schoeller, W. W.; Jutzi, P. Organometallics 1998, 17, 2149.
62. (e) Kalikhman I.; Krivonos, S.; Lameyer, L.; Stalke, D.; Kost, D. Organometallics 2001, 20, 1053.
63. (f) Kingston, V.; Gostevskii, B.; Kalikhman, I. Kost, D. Chem. Commun. 2001, 1272.
64. (g) Kost, D.; Kingston, V.; Gostevskii, B.; Ellern, A.; Stalke, D.; Walfort, B.; Kalikhman, I. Organometallics 2002, 21, 2293.
65. (h) Kalikhman, I.; Gostevskii, B.; Girshberg, O.; Krivonos, S.; Kost, D. Organometallics 2002, 21, 2551.
66. Müller, T.; Meyer, R.; Lennartz, D.; Siehl, H.-U. Angew. Chem., Int. Ed. 2000, 39, 3074.
67. Meyer, R.; Werner, K.; Müller, T. Chem.-Eur. J. 2002, 8, 3203.
68. (a) Killian, L.; Wrackmeyer, B. J. Organomet. Chem. 1978, 148, 137.
69. (b) Wrackmeyer, B.; Kundler, S.; Boese, R. Chem. Ber. 1993, 126, 1361.
70. (c) Wrackmeyer, B.; Kundler, S.; Milius, W.; Boese, R. Chem. Ber. 1994, 127, 333.
71. (d) Wrackmeyer, B.; Kehr, G.; Boese, R. Angew. Chem., Int. Ed. Engl. 1991, 30, 1370.
72. (e) Wrackmeyer, B.; Horchler, K.; Boese, R. Angew. Chem., Int. Ed. Engl. 1989, 28, 1500.
73. Steinberger, H.-U.; Müller, T.; Auner, N.; Maerker, C.; Schleyer, P. v. R. Angew. Chem., Int. Ed. Engl. 1997, 36, 626.
74. (a) Olah, G. A.; White, A. M.; DeMember, J. R.; Commeyras, A,; Lui, C. Y. J. Am. Chem. Soc. 1970, 92, 4627.
75. (b) Olah, G. A.; Prakash, G. K. S.; Arvanaghi, M.; Anet, F. A. J. Am. Chem. Soc. 1982, 104, 7105.
76. (a) Koch, W.; Liu, B.; DeFrees, D. J.; Sunko, D. E.; Vancik, H. Angew. Chem., Int. Ed. Engl. 1990, 29, 183.
77. (b) Koch, W.; Liu, B.; DeFrees, D. J. J. Am. Chem. Soc. 1989, 111, 1527.
78. (c) Schleyer, P. v. R.; Sieber, S. Angew. Chem., Int. Ed. Engl. 1993, 32, 1606.
79. 6): δ 7.09 (br, 15H), 5.41 (s. IH).
80. A similar reaction has been recently used for the synthesis of diethylalumenium from triethylaluminum: Kim, K.-C.; Reed, C. A.; Long, G. S.; Sen, A. J, Am. Chem. Soc. 2002, 124, 7662.
81. 6): δ 5.60.
82. (a) Caelingaert, G.; Soroos, H.; Shapiro, H. J. Am. Chem. Soc. 1940, 62, 1099.
83. (b) Caelingaert, G.; Soroos, H.; Shapiro, H. J. Am. Chem. Soc. 1940, 62, 1104.
84. 4] suitable crystals for X-ray analysis have been obtained; the crystal structure could however not be resolved because of severe disordering of the cations.
85. Lambert, J. B.; Zhang, S.; Ciro, S. M. Organometallics 1994, 13, 2430.
86. 6 at room temperature; see the Experimental Section.
87. Blackwell, J. M.; Piers, W. E.; McDonald, R. J. Am. Chem. Soc. 2002, 124, 1296.
88. Wrackmeyer, B. Annu. Rep. NMR Spectrosc. 1985, 16, 73.
89. Wrackmeyer, B.; Horchler, K. Annu. Rep. NMR Spectrosc. 1989, 22, 249.
90. Nadvornik, M.; Holecek, J.; Handlir, K.; Lycka, A. J. Organomet. Chem. 1984, 275, 43.
91. At lower temperatures even the toluene solution of the salt becomes solid.
92. 35
93. (a) Olah, G. A.; Donovan, D. J. J. Am. Chem. Soc. 1977, 99, 5026.
94. 13C NMR Spektroskopie; Thieme: Stuttgart, Germany, 1984.
95. 2J(CPb) = 27 Hz).
96. 0) (Rw = 0.059 for all data, 10755 reflections). GOF = 1.021. Cambridge database file CCDC-190293.
97. All calculations were performed with Gaussian 94, Revisions C2-E2, and Gaussian 98, Revisions A3-A9, Gaussian, Inc., Pittsburgh, PA, 1995 and 1999.
98. (a) Parr, R. G.; Yang, W. Density-Functional Theory of Atoms and Molecules; Oxford University Press: Oxford, 1989.
99. (b) Koch, W.; Holthausen, M. C. A Chemist's Guide to Density Functional Theory; Wiley-VCH: Weinheim, Germany, 2000.
100. (a) Becke, A. D. Phys. Rev. 1988, A 38, 3098.
101. (b) Becke, A. D. J. Chem. Phys. 1993, 98, 5648.
102. (c) Lee, C.; Yang, W.; Parr, R. G. Phys. Rev. B 1988, 37, 785.
103. Cundari, T. R.; Benson, M. T.; Lutz, M. L.; Sommerer, S. O. In Reviews in Computational Chemistry; Lipkowitz, K. B., Boyd, D. B., Eds.; VCH: New York, 1996; Vol. 8, p 145.
104. Quasirelativistic effective core potentials (ECPs): (a) Bergner, A.; Dolg, M.; Stoll, H.; Preuss, H. Mol. Phys. 1993, 80, 1431, (Si, Ge, Sn).
105. (b) Kuechle, W.; Dolg, M.; Stoll, H.; Preuss, H. Mol. Phys. 1991, 74, 1245, (Pb).
106. -1 (B3LYP/6-31G(d)//B3LYP/6-31G(d)), or 28.7 (MP2/6-311G(d,p)//MP2/6-311G(d,p)).
107. (a) Ditchfield R. Mol. Phys. 1974, 27, 789.
108. (b) Wolinski, K.; Hilton, J. F.; Pulay, P. J. Am. Chem. Soc. 1982, 104, 5667.
109. (c) Cheeseman, J. R.; Trucks, G. W.; Keith, T. A.; Frisch, M. J. J. Chem. Phys. 1996, 104, 5497.
110. (a) Møller C.; Plesset M. S. Phys. Rev. 1934, 46, 618.
111. (b) Head-Gordon, M.; Pople, J. A.; Frisch, M. Chem. Phys. Lett. 1988, 153, 503.
112. (a) NBO 4.0: Glendening, E. D.; Badenhoop, J. K.; Reed, A. E.; Carpenter, J. E.; Weinhold, F. Theoretical Chemistry Institute, University of Wisconsin, Madison, WI, 1996.
113. (b) Reed, A. E.; Curfiss, L. A.; Weinhold, F. Chem. Rev. 1988, 88, 899.
114. For an introduction see: Hehre, W. J.; Radom, L.; Schleyer, P. v. R.; Pople, J. A. Ab initio molecular orbital theory; Wiley-Interscience: New York, 1986.
115. + ions (E = C-Pb, X = F-I): Frenking, G.; Fau, S.; Marchand, C. M.; Grützmacher, H. J. Am. Chem. Soc. 1997, 119, 6648.
116. + ions (E = C-Pb, X = H, Me, Cl): Basch, H. Inorg. Chim. Acta 1996, 242, 191.
117. -1.
118. -1. Hobza, P.; Sponer, J.; Reschel, T. J. Comput. Chem. 1995, 16, 1315.
119. (a) Kestner, N. R. J. Chem. Phys. 1968, 48, 252.
120. (b) Liu, B.; McLean, A. D. J. Chem. Phys. 1973, 59, 4557.
121. (c) Boys, S. F.; Bernardi, F. Mol. Phys. 1970, 19, 553.
122. -1.
123. Review: Schleyer, P. v. R.; Marker, C. Pure Appl. Chem. 1995, 67, 755.
124. 13C) = 3.7 ± 1.5, 24 data points, correlation coefficient 0.996; for details see the Supporting Information.
125. (a) Ottoson, C.-H.; Cremer, D. Organometallics 1996, 15, 5495.
126. (b) For a short review see: Webb, G. A. In Enzyclopedia of NMR Spectroscopy; Grant, D., Webb, G. A., Eds.; Wiley: New York. 1996; p 4316.
127. (a) Gauss, J. Chem. Phys. Lett. 1992, 191, 614.
128. (b) Gauss, J. J. Chem. Phys. 1993, 99, 3629.
129. (c) Gauss, J.; Stanton, J. F. J. Chem. Phys. 1996, 104, 2574.
130. (a) Siehl, H.-U.; Müller, T.; Gauss, J.; Buzek, P.; Schleyer, P. v. R. J. Am. Chem. Soc. 1994, 116, 6384.
131. (b) Stanton, J. F.; Gauss, J.; Siehl, H.-U. Chem. Phys. Lett. 1996, 262, 183;
132. (c) Apeloig, Y.; Müller, T. In Dicoordinated Carbocations; Rappoport, Z., Stang, P. J., Eds.; Wiley: New York, 1997; Chapter 2, p 9.
133. Buzek, P.; Schleyer, P. v. R.; Vancik, H.; Mihalic, Z.; Gauss, J. Angew. Chem., Int. Ed. Engl. 1994, 33, 448.
134. Sieber, S.; Schleyer, P. v. R.; Gauss, J. J. Am. Chem. Soc. 1993, 115, 6987.
135. (a) Hosomi, A.; Mikami, M.; Sakurai, H. Bull. Chem. Soc. Jpn. 1983, 56, 2784.
136. (b) Bauch, C. Master Thesis, Goethe Universität Frankfurt/Main, 2000.
137. (c) Ostermeier, M. Master Thesis, Goethe Universität Frankfurt/Main, 1999.
138. (a) Massey, A. G.; Park, A. J. J. Organomet. Chem. 1964, 245.
139. (b) Chien, J. C. W.; Tsai, W.-M.; Rausch, M. D. J. Am. Chem. Soc. 1991, 113, 8570.