Planar-tetracoordinate carbon in a neutral saturated hydrocarbon: Theoretical design and characterization

Angewandte Chemie - International Edition

Volumn 38, Issue 19, 1999, Pages 2875-2878

  Rasmussen, Danne R ^a   Radom, Leo ^a  

^a AUSTRALIAN NATIONAL UNIVERSITY   (Australia)

Author keywords

Ab initio calculations; Cage compounds; Hydrocarbons; Ionization potentials; Planar tetracoordinate carbon

Indexed keywords

METHANE; NEOPENTANE; UNCLASSIFIED DRUG;

ARTICLE; CHEMICAL STRUCTURE; ENANTIOMER; ENERGY COST; MATHEMATICAL COMPUTING; ORGANIC CHEMISTRY; RACEMIC MIXTURE; STRUCTURE ANALYSIS;

EID: 0033523603     PISSN: 14337851     EISSN: None     Source Type: Journal    
DOI: 10.1002/(sici)1521-3773(19991004)38:19<2875::aid-anie2875>3.0.co;2-d     Document Type: Article

References (48)

1. a) J. H. van't Hoff, Arch. Neerl. Sci. Exactes Nat. 1874, 9, 445-454; English translation: J. H. van't Hoff in Classics in the Theory of Chemical Combinations, Vol. I (Ed.: O. T. Benfey), Dover, New York, 1963, pp. 151-160;
2. a) J. H. van't Hoff, Arch. Neerl. Sci. Exactes Nat. 1874, 9, 445-454; English translation: J. H. van't Hoff in Classics in the Theory of Chemical Combinations, Vol. I (Ed.: O. T. Benfey), Dover, New York, 1963, pp. 151-160;
3. b) J. A. Le Bel, Bull. Chim. Soc. Fr. 1874, 22, 337-347; English translation: J. A. Le Bel in Classics in the Theory of Chemical Combinations, Vol. I (Ed.: O. T. Benfey), Dover, New York, 1963, pp. 161-171.
4. b) J. A. Le Bel, Bull. Chim. Soc. Fr. 1874, 22, 337-347; English translation: J. A. Le Bel in Classics in the Theory of Chemical Combinations, Vol. I (Ed.: O. T. Benfey), Dover, New York, 1963, pp. 161-171.
5. a) R. Hoffmann, R. Alder, C. F. Wilcox, Jr. J. Am. Chem. Soc. 1970, 92, 4992-4993;
6. b) R. Hoffmann, Pure Appl Chem. 1971, 28, 181-194.
7. See, for example, a) J. B. Collins, J. D. Dill, E. D. Jemmis, Y. Apeloig, P. von R. Schleyer, R. Seeger, J. A. Pople, J. Am. Chem. Soc. 1976, 98, 5419-5427;
8. b) K. Krogh-Jesperson, D. Cremer, D. Poppinger, J. A. Pople, P. von R. Schleyer, J. Chandrasekhar, J. Am. Chem. Soc. 1979, 101, 4843-4851;
9. c) K. Sorger, P. von R. Schleyer, J. Mol. Struct. Theochem. 1995, 338, 317-346.
10. See, for example, a) F. A. Cotton, M. Millar, J. Am. Chem. Soc. 1977, 99, 7886-7891;
11. b) H. Dietrich, W. Mahdi, W. Storck, J. Organomet. Chem. 1988, 349, 1-10;
12. c) S. Harder, J. Boersma, L. Brandsma, A. van Heteren, J. A. Kanters. W. Bauer, P. von R. Schleyer, J. Am. Chem. Soc. 1988, 110, 7802-7806;
13. d) S. L. Buchwald, E. A. Lucas, W. M. Davies, J. Am. Chem. Soc. 1989, 111, 397-398;
14. e) S. T. Chacon, M. H. Chisholm, K. Folting, J. C. Huffman, M. J. Hampden-Smith, Organometallics 1991, 10, 3722-3735;
15. f) A. D. Horton, A. G. Orpen, Angew. Chem. 1992, 104, 912; Angew. Chem. Int. Ed. Engl. 1992, 31, 876-878.
16. f) A. D. Horton, A. G. Orpen, Angew. Chem. 1992, 104, 912; Angew. Chem. Int. Ed. Engl. 1992, 31, 876-878.
17. See also a) M. Albrecht, G. Erker, C. Krüger, Synlett 1993, 441-448;
18. b) R. Gleiter, I. Hyla-Kryspin, S. Niu, G. Erker, Angew. Chem. 1993, 105, 753; Angew. Chem. Int. Ed. Engl. 1993, 32, 754-756;
19. b) R. Gleiter, I. Hyla-Kryspin, S. Niu, G. Erker, Angew. Chem. 1993, 105, 753; Angew. Chem. Int. Ed. Engl. 1993, 32, 754-756;
20. c) D. Röttger, G. Erker, Angew. Chem. 1997, 109, 840-856; Angew. Chem. Int. Ed. Engl. 1997, 36, 813-827;
21. c) D. Röttger, G. Erker, Angew. Chem. 1997, 109, 840-856; Angew. Chem. Int. Ed. Engl. 1997, 36, 813-827;
22. d) J. Schottek, G. Erker, R. Fröhlich, Eur. J. Inorg. Chem. 1998, 551-558.
23. B. W. Ding, R. Keese, H. Stoeckli-Evans, Angew. Chem. 1999, 111, 387-388; Angew. Chem. Int. Ed. 1999, 38, 375-376.
24. B. W. Ding, R. Keese, H. Stoeckli-Evans, Angew. Chem. 1999, 111, 387-388; Angew. Chem. Int. Ed. 1999, 38, 375-376.
25. For representative studies, see a) K. B. Wiberg, Tetrahedron Lett. 1985, 26, 5967-5970;
26. b) W. C. Agosta in The Chemistry of Alkanes and Cycloalkanes (Eds.: S. Patai, Z. Rappoport), Wiley, New York, 1992, pp. 927-962;
27. c) M. Thommen, R. Keese, Synlett 1997, 231-240.
28. W. J. Hehre, L. Radom, P. von R. Schleyer, J. A. Pople, Ab Initio Molecular Orbital Theory, Wiley, New York, 1986.
29. a) M. S. Gordon, M. W. Schmidt, J. Am. Chem. Soc. 1993, 115, 7486-7492;
30. b) M. J. M. Pepper, I. Shavitt, P. von R. Schleyer, M. N. Glukhovtsev, R. Janoschek, M. Quack, J. Comput. Chem. 1995, 16, 207-225.
31. Detailed results and more extensive references will be published elsewhere: D. R. Rasmussen, M. P. McGrath, L. Radom, unpublished results.
32. a) M. P. McGrath, L. Radom, J. Am. Chem. Soc. 1993, 115, 3320-3321;
33. b) J. E. Lyons, D. R. Rasmussen, M. P. McGrath, R. H. Nobes, L. Radom, Angew. Chem. 1994, 106, 1722; Angew. Chem. Int. Ed. Engl. 1994, 33, 1667-1668.
34. b) J. E. Lyons, D. R. Rasmussen, M. P. McGrath, R. H. Nobes, L. Radom, Angew. Chem. 1994, 106, 1722; Angew. Chem. Int. Ed. Engl. 1994, 33, 1667-1668.
35. M. J. Frisch, G. W. Trucks, H. B. Schlegel, P. M. W. Gill, B. G. Johnson, M. A. Robb, J. R. Cheeseman, T. Keith, G. A. Petersson, J. A. Montgomery, K. Raghavachari, M. A. Al-Laham, V. G. Zakrzewski, J. V. Ortiz, J. B. Foresman, J. Cioslowski, B. B. Stefanov, A. Nanayakkara, M. Challacombe, C. Y. Peng, P. Y. Ayala, W. Chen, M. W. Wong, J. L. Andres, E. S. Replogle, R. Gomperts, R. L. Martin, D. J. Fox, J. S. Binkley, D. J. Defrees, J. Baker, J. P. Stewart, M. Head-Gordon, C. Gonzalez, J. A. Pople, Gaussian 94, Revision E.2, Gaussian, Inc., Pittsburgh PA, 1995.
36. 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, M. Dupuis, J. A. Montgomery, Jr., J. Comput. Chem. 1993, 14, 1347-1363.
37. [10] In particular, we find that diffuse functions on the central atom significantly lower the relative energies of the planar versus the tetrahedral species. The 6-311+G(2d,p) basis was found to be the smallest basis set which adequately approaches the basis set limit for this energy difference. As might have been expected, calculations on alkaplanes indicate that the full 6-311+G(2d,p) basis can be well approximated by using a 6-31G(d) basis which is enhanced to 6-311+G(2d) level at the central carbon atom and to the 6-311+G(d) level at the four α-carbon atoms, thus significantly reducing the size of the calculations. Optimization in the full 6-311+G(2d,p) basis (765 basis functions for 3) is beyond our current computational resources.
38. Energies for the potential functions were calculated at the MP2/6-311+G(2d,p) level using the full 6-311+G(2d,p) basis on all atoms. Geometries were optimized at the HF/6-31G(d) level.
39. -1.
40. This 435 basis function calculation took 32000 node hours on a Cray T3E at the CEWES High Performance Computing Center! D. R. Rasmussen, M. S. Gordon, L. Radom, unpublished results.
41. V. B. Rao, C. F. George, S. Wolff, W. C. Agosta, J. Am. Chem. Soc. 1985, 107, 5732-5739.
42. [20] However, it would seem difficult for this to occur within the extremely rigid constraints of the cage system.
43. a) R. Herges, personal communication;
44. b) R. Herges, Angew. Chem. 1994, 106, 261; Angew. Chem. Int. Ed. Engl. 1994, 33, 255-276.
45. b) R. Herges, Angew. Chem. 1994, 106, 261; Angew. Chem. Int. Ed. Engl. 1994, 33, 255-276.
46. H. Prinzbach, K. Weber, Angew. Chem. 1994, 106, 2329; Angew. Chem. Int. Ed. Engl. 1994, 33, 2239-2257, and references therein.
47. H. Prinzbach, K. Weber, Angew. Chem. 1994, 106, 2329; Angew. Chem. Int. Ed. Engl. 1994, 33, 2239-2257, and references therein.
48. [11b]