The remarkably stabilized trilithiocyclopropenium ion, C3Li3+, and its relatives

Journal of the American Chemical Society

Volumn 119, Issue 40, 1997, Pages 9504-9512

  Jemmis, Eluvathingal D ^a   Subramanian, Govindan ^a   Kos, Alexander J ^a   Schleyer, Paul V R ^a  

^a NONE

Author keywords

[No Author keywords available]

Indexed keywords

ORGANOLITHIUM COMPOUND;

ARTICLE; DRUG STRUCTURE; ENERGY; MAGNETISM; MOLECULAR STABILITY; NUCLEAR MAGNETIC RESONANCE SPECTROSCOPY; THERMODYNAMICS;

EID: 0030830808     PISSN: 00027863     EISSN: None     Source Type: Journal    
DOI: 10.1021/ja970589a     Document Type: Article

References (109)

1. (a) Jemmis, E. D.; Chandrasekhar, J.; Schleyer, P. v. R. J. Am. Chem. Soc. 1979, 101, 527.
2. (b) Chandrasekhar, J.; Pople, J. A.; Seeger, R.; Seeger, U.; Schleyer, P. v. R. J. Am. Chem. Soc. 1982, 104, 3651.
3. (a) Wu, C. H.; Ihle, H. R. Chem. Phys. Lett. 1979, 61, 54.
4. (b) Kudo, H. Chem. Lett. 1989, 1611.
5. (a) Apeloig, Y.; Schleyer, P. v. R.; Pople, J. A. J. Am. Chem. Soc. 1977, 99, 1291.
6. (b) Schleyer, P. v. R. Pure Appl. Chem. 1983, 55, 355; 1984, 56, 151; 1987, 59, 1647. Also see ref 8.
7. (b) Schleyer, P. v. R. Pure Appl. Chem. 1983, 55, 355; 1984, 56, 151; 1987, 59, 1647. Also see ref 8.
8. (b) Schleyer, P. v. R. Pure Appl. Chem. 1983, 55, 355; 1984, 56, 151; 1987, 59, 1647. Also see ref 8.
9. (a) Collins, J. B., Dill, J. D.; Jemmis, E. D.; Apeloig, Y.; Schleyer, P. v. R.; Seeger, R.; Pople, J. A. J. Am. Chem. Soc. 1976, 98, 5419.
10. (b) temmis, E. D.; Chandrasekhar, J.; Würthwein, E-.U.; Schleyer, P. v. R.; Chinn, J. W., Jr.; Landro, F. J.; Lagow, R. J.; Luke, B. T.; Pople, J. A. J. Am. Chem. Soc. 1982, 104, 4275.
11. Schleyer, P. v. R.; Tidor, B.; Jemmis, E. D.; Chandrasekhar, J.; Würthwein, E-.U.; Kos, A. J.; Luke, B. T.; Pople, J. A. J. Am. Chem. Soc. 1983, 105, 484.
12. Reed, A. E.; Weinhold, A. J. Am. Chem. Soc. 1985, 107, 1919.
13. (e) Bolton, E. E.; Schaefer, H. F., III.; Laidig, W. D.; Schleyer, P. v. R. J. Am. Chem. Soc. 1994, 116, 9602.
14. (a) Shimp, L. A.; Lagow, R. J. J. Am. Chem. Soc. 1979, 101, 2214.
15. (b) Gurak, J. A.; Chinn, J. W., Jr.; Lagow, R. J. J. Am. Chem. Soc. 1982, 104, 2637.
16. Shimp, L. A.; Morrisson, J. A.; Lagow, R. J.; Gurak, J. A.; Chinn, J. W., Jr. J. Am. Chem. Soc. 1982, 103, 5951.
17. Chinn, J. W., Jr.; Lagow, R. J. Organometallics 1984, 3, 75.
18. (e) Chinn, J. W., Jr.; Lagow, R. J. J. Am. Chem. Soc. 1984, 706, 3694.
19. (f) Chinn, J. W., Jr.; Gurak, J. A.; Lagow, R. J. In Lithium: Current Applications in Science, Medicine and Technology, Bach, R. O., Ed.; Wiley: New York, 1986; Chapter 20, p 29.
20. (g) Lagow, R. J.; Gurak, J. A. In IUPAC Chemistry for the Future; Gruenwald, Ed.; Pergamon Press: Oxford, 1984.
21. (a) Maercker, A.; Thies, M. In Topics In Current Chemistry; Springer-Verlag: Heidelberg, Germany, 1987; Vol. 138.
22. (b) For reviews on organolithium compounds, see: Lithium Chemistry; Sapse, A.-M, Schleyer, P. v. R., Eds.; Wiley: New York, 1995.
23. Ivanic, J.; Marsden, C. J. Am. Chem. Soc. 1993, 115, 7503.
24. Jemmis, E. D.; Chandrasekhar, J.; Schleyer, P. v. R. J. Am. Chem. Soc. 1989, 101, 2848.
25. (a) Weiss, R.; Priesner, C. Angew. Chem., Int. Ed. Engl. 1978, 17, 445.
26. (b) Weiss, R.; Priesner, C.; Wolf, H. Angew. Chem., Int. Ed. Engl. 1978, 77, 446.
27. Hehre, W. J.; Radom, L.; Schleyer, P. v. R.; Pople, J. A. Ab Initio Molecular Orbital Theory; Wiley: New York, 1986; p 348.
28. (a) Krogh-Jesperson, K.; Cremer, D.; Dill, J. D.; Pople, J. A.; Schleyer, P. v. R. J. Am. Chem. Soc. 1981, 103, 2589.
29. (b) Wong, M. W.; Radom, L. J. Am. Chem. Soc. 1989, 111, 6976.
30. Glukhovtsev, M. N.; Laiter, S.; Pross, A. J. Phys. Chem. 1996, 100, 17801.
31. Korth, A.; Marconi, M. L.; Mendis, D. A.; Krueger, F. R.; Richter, A. K.; Lin, R. P.; Mitchel, D. L.; Anderson, K. A.; Carlson, C. W.; Reme, H.; Sauvaud, J. A.; d'Uston, C. Nature 1989, 337, 53.
32. (a) Rauscher, G.; Clark, T.; Poppinger, D.; Schleyer, P. v. R. Angew. Chem., Int. Ed. Engl. 1978, 17, 276.
33. (b) Dill, J. D.; Greenberg, A.; Liebman, J. F. J. Am. Chem. Soc. 1979, 101, 6814.
34. Ritchie, J. P.; J. Am. Chem. Soc. 1983, 105, 2083.
35. Disch, R. L.; Schulman, J. M.; Ritchie, J. P. J. Am. Chem. Soc. 1984, 106, 6246.
36. (e) Schleyer, P.v. R. J. Phys. Chem. 1990, 94, 5560. At MP2(FULL)/6-31G*and at Becke3LYP/6-311+G*, tetralithiotetrahedrane is a local minimum contrary to the lower level results in refs 11c,d.
37. (a) Hopkinson, A. C.; Lien, M. H. Can. J. Chem. 1985, 63, 3582.
38. (b) Hopkinson, A. C.; Lien, M. H. J. Am. Chem. Soc. 1986, 108, 2843.
39. Lien, M. H.; Hopkinson, A. C. J. Mol. Struct. (THEOCHEM) 1988, 165, 37.
40. Lien, M. H.; Hopkinson, A. C. J. Mol. Struct. (THEOCHEM) 1985, 127, 1.
41. (a) Lee, C.; Yang, W.; Parr, R. G. Phys. Rev. 1988, B37, 785.
42. (b) Becke, A. D. Phys. Rev. 1988, A38, 3098.
43. Becke, A. D. J. Chem. Phys. 1993, 98, 5648.
44. For details of basis sets see ref 8 and the following: Foresman, J. B.; Frisch, Æ. Exploring Chemistry with Electronic Structure Methods: A Guide to using Gaussian, 2nd ed.; Gaussian Inc.: Pittsburgh, PA, 1996.
45. Frisch, M J.; Trucks, G. W.; Schlegel, H. B.; Gill, P. M. W.; Johnson, B. G.; Robb, M. A.; Cheeseman, J. R.; Keith, T.; Peterson, J. A.; Montgomerry, J. A.; Raghavachari, K.; Al-Laham, M. A.; Zakrzewski, V. G.; Ortiz, J. Y.; Foresman, J. B.; Cioslowski, J.; Stefanov, B. B.; Nanayakkara, A.; Challacombe, M.; Peng, C. Y.; Ayala, P. Y.; Chen, W.; Wong, M. W.; Andres, J.I., Replogle, E. S.; Gomperts, R.; Martin, R. L.; Fox, D. J.; Binkley, J. S.; DeFrees, D. J.; Baker, J.; Stewart, J. J. P.; Head-Gordon, M.; Gonzalez, C.; Pople, J. A. Gaussian 94, Ver. C.4, Gaussian Inc.: Pittsburgh, PA, 1995.
46. (a) Binkley, J. S.; Pople, J. A.; Hehre, W. J. J. Am. Chem. Soc. 1980, 102, 939.
47. (b) Gordon, M. S.; Binkley, J. S., Pople, J. A.; Pietro, N. J.; Hehre, W. J. J. Am. Chem. Soc. 1982, 104, 2797.
48. (a) Radom, L.; Hariharan, P. C.; Pople, J. A.; Schleyer, P. v. R. J. Am. Chem. Soc. 1973, 95, 6531.
49. Ibid. 1976, 98, 10.
50. (b) Raghavachari, K.; Whiteside, R. A.; Pople, J. A.; Schleyer, P. v. R. J. Am. Chem. Soc. 1981, 103, 5649.
51. Cameron, A., Leszczynski, J.; Zerner, M. C., Weiner, B. J. Phys. Chem. 1989, 93, 139.
52. Lee, T. J.; Willetts, A.; Gaw, J. F.; Handy, N. C. J. Chem. Phys. 1989, 90, 4330.
53. (e) Li, W.-K.; Riggs, N. V. J. Mol. Struct. (THEOCHEM) 1992, 257, 189.
54. (f) Jemmis, E. D.; Subramanian, G.; Srinivas, G. N. J. Am. Chem. Soc. 1992, 114, 7939.
55. (g) Wong, M. W.; Radom. L. J. Am. Chem. Soc. 1993, 115, 1507.
56. (h) Galembeck, S. E.; Fausto, R. J. Mol. Struct, (THEOCHEM) 1995, 332, 105.
57. (a) Xie, Y.; Schaefer, H. F., III. Chem. Phys. Lett. 1991, 179, 563.
58. (b) Smith, B. J. Chem. Phys. Lett. 1994, 207, 403.
59. Also see refs 3, 6b, and 8.
60. (a) Binkley, J. S.; Pople, J. A., Int. J. Quantum. Chem. 1975, 9, 229 and references therein,
61. (b) Pople, J. A.; Binkley, J. S.; Seeger, R. Int. J. Quantum. Chem. Symp. 1976, 10, 1 and references therein.
62. (a) The ΔH in eqs 1-20 includes the HF/6-31G*zero-point energies (scaled by a factor of 0.89 and applied to the HF, MP2, and MP4 total energies). For details, see: Pople, J. A.; Krishnan, R.; Schlegel, H. B.; Binkley, J. S. Int. J. Quantum Chem. Symp. 1979, 13, 225.
63. (b) Krishnan, R.; Schlegel, H. B.; Binkley, J. S.; Whiteside, R. A.; Frisch, M. J.; Pople, J. A.; Hout, R. F., Jr.; Hehre, W. J. Int. J. Quantum Chem. Symp. 1981, 15, 269.
64. No scaling factor for the Becke3LYP/6-311+G*zero-point energies were used in eqs 1-20. See: Schleyer, P. v. R.; Jiao, H.; Glukhovtsev, M.; Chandrasekhar, J.; Kraka, E. J. Am. Chem. Soc. 1994, 116, 10129.;
65. Reed, A. E.; Weinhold, F.; Curtiss, L. A. Chem. Rev. 1988, 88, 899 and references therein.
66. (a) Breslow, R.; Groves, J. T.; Ryan, G. J. Am. Chem. Soc. 1967, 89, 5048.
67. (b) Farnum, D. G.; Mehta, G.; Silberman, R. G. J. Am. Chem. Soc. 1967, 89, 5048.
68. Breslow, R.; Groves, J. T. J. Am. Chem. Soc. 1970, 92, 984.
69. Lossing, F. P. Can. J. Chem. 1972, 50, 3973.
70. (e) Ausloos, P. J.; Lias, S. G. J. Am. Chem. Soc. 1981, 103, 6505.
71. Lias, S. G.; Bartmess, J. E.; Liebmann, J. F.; Holmes, J. C.; Levin, R. D.; Mallard, W. G. J. Phys. Chem. Ref. Data 1988, 17, Suppl. 1.
72. Sorger, K.; Schleyer, P.v. R.; Stalke, D. J. Am. Chem. Soc. 1996, 118, 1086.
73. (a) Bernardi, F.; Bottoni, A.; Venturini, A. J. Am. Chem. Soc. 1986, 108, 5395.
74. (b) Kapp, J.; Schade, C; El-Nahasa, A. M.; Schleyer, P. v. R. Angew. Chem., Int. Ed. Engl. 1996, 35, 2236 and references therein.
75. Apeloig, Y.; Schleyer, P. v. R.; Pople, J. A. J. Am. Chem. Soc. 1977, 99, 5901.
76. Bent, H. A. Chem. Rev. 1961, 66, 275.
77. (a) Yoshida, Z.-i.; Tawara, Y. J. Am. Chem. Soc. 1971, 93, 2573.
78. (b) Ku, A. T.; Sundaralingam, M. J. Am. Chem. Soc. 1972, 94, 1688.
79. Wolinski, K.; Hinton, J. F.; Pulay, P. J. Am. Chem. Soc. 1990, 112, 8251.
80. Breitmaier, E.; Jung, G. Organische Chemie U. Spezielle Verbindungsklassen, Naturstoffe, Synthesen, Structurauflärung; Georg Thieme Verlag: Stuttgart, Germany, 1995.
81. (a) Pople, J. A. J. Chem. Phys. 1956, 24, 1111.
82. (b) Dauben, H. J., Jr.; Wilson, J. D.; Laity, J. L. J. Am. Chem. Soc. 1969, 91, 1991.
83. Benson, R. C.; Flygare, W. H. J. Am. Chem. Soc. 1970, 92, 7523.
84. Katritzky, A. R.; Barczynski, P.; Musumarr, G.; Pisano, D.; Szafran, M. J. Am. Chem. Soc. 1989, 111, 7.
85. (e) Jug, K.; Köster, A. M. J. Phys. Org. Chem. 1991, 4, 163.
86. (f) Minkin, W. I.; Glukhovtsev, M. N.; Simkin, B. Ya. Aromaticity and Antiaromaticity; Wiley-Interscience: New York, 1994.
87. (g) Schleyer, P. v. R.; Freemann, P.; Jiao, H.; Goldfuss, B. Angew. Chem., Int. Ed. Engl. 1995, 34, 337.
88. (h) Schleyer, P. v. R.; Jiao, H. Pure Appl. Chem. 1996, 68, 209.
89. Schleyer, P. v. R.; Maerker, C.; Dransfeld, A.; Jiao, H.; Hommes, N. J. v. E. J. Am. Chem. Soc. 1996, 118, 6317.
90. (j) Bird, C. W. Tetrahedron 1996, 52, 9945.
91. Fleischer, U.; Kutzelnigg, W.; Lazzeretti, P.; Mühlenkamp, V. J. Am. Chem. Soc. 1994, 116, 5298.
92. NICS is defined as the negative of the absolute magnetic shieldings computed, for example, at the unweighted geometric center of aromatic or antiaromatic rings [NICS(0)] or 1 Å above the ring [NICS(1)]. Significantly negative NICS values indicate the presence of diatropic ring current and, therefore, aromaticity in the systems.
93. (a) Craig, N. C.; Pranata, J.; Reinganum, S. J.; Sprague, J. R.; Stevens, P. S. J. Am. Chem. Soc. 1986, 108, 4378 and references therein,
94. (b) Galembeck, S. E.; Fausto, R. J. Mol. Struct. (THEOCHEM) 1995, 332, 105.
95. (a) The experimental ionization energies are taken from the following: McMillen, D. F.; Golden, D. M. Annu. Rev. Phys. Chem. 1982, 33, 493 for the cydopropenyl radical
96. (b) For an excellent compilation of the reported IE's in literature, see ref 23.
97. Weiss, R.; Schlierf, C; Schloter, K. J. Am. Chem. Soc. 1976, 98, 4668.
98. (a) Apeloig, Y. In The Chemistry of Organosilicon Chemistry, Patai, S., Rappoport, Z., Eds.; J. Wiley and Sons Ltd.: London, 1989.
99. (b) Maerker, C.; Kapp, J.; Schleyer, P. v. R. In Organosilicon Chemistry II; Auner, N., Weis, J., Eds.; VCH: Weinheim, Germany, 1996.
100. (a) Maier, G.; Volz, D.; Neudert, J. Synthesis 1992, 561.
101. (b) de Meijere, A.; Faber, D.; Noltemeyer, M; Boese, R.; Haumann, T.; Müller, T.; Bendikov, M.; Matzner, E.; Apeloig, Y. J. Org. Chem. 1996, 61, 8564.
102. Morton, M. S.; Selegue, J. P. J. Am. Chem. Soc. 1995, 117, 7005.
103. Re, N.; Sgamellotti, A.; Floriani, C. Organometallics 1996, 15, 5330.
104. (a) Scherbaum, R; Grohmann, A.; Huber, B.; Krüger, C; Schmidbaur, H. Angew. Chem., Int. Ed. Engl. 1988, 27, 1544.
105. (b) Schmidbaur, H. Chem. Soc. Rev. 1995, 24, 391.
106. (a) Yoshida, Z.; Konishi, H.; Tamaru, Y.; Nishikawa, K.; Ogoshi, H. Tetrahedron Lett., 1973, 2619.
107. (b) Yoshida, Z.; Konishi, H.; Miura, Y.; Ogoshi, H. Tetrahedron Lett. 1977, 4319.
108. Yoshida, Z.; Konishi, H.; Sawada, S.; Ogoshi, H. J. Chem. Soc. Chem. Commun. 1977, 850.
109. Although the classical 1,2-dilithiocyclopropene is a stationary point at HF/STO-3G (Jemmis, E. D.; Chandrasekhar, J.; Schleyer, P. v. R. J. Am. Chem. Soc. 1979, 101, 2848), the dibridged isomer (26) is 16.3 kcal/ mol more stable. However, the classical structure collapses to 26 at higher levels of theory (for example, HF/3-21G and B3LYP/6-311+G*).