Ab initio calculations on the preferred mode of ring opening in silacyclopropane

Journal of the American Chemical Society

Volumn 119, Issue 34, 1997, Pages 8012-8014

  Skancke, Per N ^a,b   Hrovat, David A ^a   Borden, Weston Thatcher ^a  

^a UNIVERSITY OF WASHINGTON   (United States)

^b UNIVERSITY OF TROMSØ   (Norway)

Author keywords

[No Author keywords available]

Indexed keywords

CYCLOPROPANE DERIVATIVE; SILANE DERIVATIVE;

ARTICLE; CALCULATION; CHEMICAL BOND; CHEMICAL MODIFICATION; ENERGY; REACTION ANALYSIS;

EID: 0030845856     PISSN: 00027863     EISSN: None     Source Type: Journal    
DOI: 10.1021/ja964384y     Document Type: Article

References (30)

1. An extensive list of references prior to 1992 can be found in the following: Getty, S. J.; Davidson, E. R.; Borden, W. T. J. Am. Chem. Soc. 1992, 114, 2085.
2. The following theoretical and experimental papers have appeared since 1992: (a) Baldwin, J. E.; Yamaguchi, Y.; Schaefer, H. F., III J. Phys. Chem. 1994, 98, 7513. (b) Pedersen, S.; Herek, J. L.; Zewail, A. H. Science 1994, 266, 1359. (c) Doubleday, C., Jr. J. Phys. Chem. 1996, 100, 3520. (d) Doubleday, C., Jr.; Bolton, K.; Peslherbe, G. H.; Hase, W. L. J. Am. Chem. Soc. 1996, 118, 9923. (e) Doubleday, C., Jr.; Bolton, K.; Hase, W. L. J. Am. Chem. Soc. 1997, 118, 5251. (f) Hrovat, D. A.; Fang, S.; Borden, W. T.; Carpenter, B. K. J. Am. Chem. Soc. 1997, 119, 5253.
3. The following theoretical and experimental papers have appeared since 1992: (a) Baldwin, J. E.; Yamaguchi, Y.; Schaefer, H. F., III J. Phys. Chem. 1994, 98, 7513. (b) Pedersen, S.; Herek, J. L.; Zewail, A. H. Science 1994, 266, 1359. (c) Doubleday, C., Jr. J. Phys. Chem. 1996, 100, 3520. (d) Doubleday, C., Jr.; Bolton, K.; Peslherbe, G. H.; Hase, W. L. J. Am. Chem. Soc. 1996, 118, 9923. (e) Doubleday, C., Jr.; Bolton, K.; Hase, W. L. J. Am. Chem. Soc. 1997, 118, 5251. (f) Hrovat, D. A.; Fang, S.; Borden, W. T.; Carpenter, B. K. J. Am. Chem. Soc. 1997, 119, 5253.
4. The following theoretical and experimental papers have appeared since 1992: (a) Baldwin, J. E.; Yamaguchi, Y.; Schaefer, H. F., III J. Phys. Chem. 1994, 98, 7513. (b) Pedersen, S.; Herek, J. L.; Zewail, A. H. Science 1994, 266, 1359. (c) Doubleday, C., Jr. J. Phys. Chem. 1996, 100, 3520. (d) Doubleday, C., Jr.; Bolton, K.; Peslherbe, G. H.; Hase, W. L. J. Am. Chem. Soc. 1996, 118, 9923. (e) Doubleday, C., Jr.; Bolton, K.; Hase, W. L. J. Am. Chem. Soc. 1997, 118, 5251. (f) Hrovat, D. A.; Fang, S.; Borden, W. T.; Carpenter, B. K. J. Am. Chem. Soc. 1997, 119, 5253.
5. The following theoretical and experimental papers have appeared since 1992: (a) Baldwin, J. E.; Yamaguchi, Y.; Schaefer, H. F., III J. Phys. Chem. 1994, 98, 7513. (b) Pedersen, S.; Herek, J. L.; Zewail, A. H. Science 1994, 266, 1359. (c) Doubleday, C., Jr. J. Phys. Chem. 1996, 100, 3520. (d) Doubleday, C., Jr.; Bolton, K.; Peslherbe, G. H.; Hase, W. L. J. Am. Chem. Soc. 1996, 118, 9923. (e) Doubleday, C., Jr.; Bolton, K.; Hase, W. L. J. Am. Chem. Soc. 1997, 118, 5251. (f) Hrovat, D. A.; Fang, S.; Borden, W. T.; Carpenter, B. K. J. Am. Chem. Soc. 1997, 119, 5253.
6. The following theoretical and experimental papers have appeared since 1992: (a) Baldwin, J. E.; Yamaguchi, Y.; Schaefer, H. F., III J. Phys. Chem. 1994, 98, 7513. (b) Pedersen, S.; Herek, J. L.; Zewail, A. H. Science 1994, 266, 1359. (c) Doubleday, C., Jr. J. Phys. Chem. 1996, 100, 3520. (d) Doubleday, C., Jr.; Bolton, K.; Peslherbe, G. H.; Hase, W. L. J. Am. Chem. Soc. 1996, 118, 9923. (e) Doubleday, C., Jr.; Bolton, K.; Hase, W. L. J. Am. Chem. Soc. 1997, 118, 5251. (f) Hrovat, D. A.; Fang, S.; Borden, W. T.; Carpenter, B. K. J. Am. Chem. Soc. 1997, 119, 5253.
7. The following theoretical and experimental papers have appeared since 1992: (a) Baldwin, J. E.; Yamaguchi, Y.; Schaefer, H. F., III J. Phys. Chem. 1994, 98, 7513. (b) Pedersen, S.; Herek, J. L.; Zewail, A. H. Science 1994, 266, 1359. (c) Doubleday, C., Jr. J. Phys. Chem. 1996, 100, 3520. (d) Doubleday, C., Jr.; Bolton, K.; Peslherbe, G. H.; Hase, W. L. J. Am. Chem. Soc. 1996, 118, 9923. (e) Doubleday, C., Jr.; Bolton, K.; Hase, W. L. J. Am. Chem. Soc. 1997, 118, 5251. (f) Hrovat, D. A.; Fang, S.; Borden, W. T.; Carpenter, B. K. J. Am. Chem. Soc. 1997, 119, 5253.
8. Apeloig, Y. In The Chemistry of Organic Silicon Compounds; Patai, S., Rappoport, Z., Eds.; Wiley: New York, 1989; Vol. 1, pp 57-226.
9. Dickinson, A. P.; O'Neal, H. E.; Ring, M. A. Organometallics 1991, 10, 3513 and references therein.
10. Møller, C.; Plesset, M. S. Phys. Rev. 1934, 46, 618.
11. CASPT2N uses second-order, multi-reference perturbation theory to recover the correlation energy that is not recovered variationally in the active space. See: (a) Anderson, K.; Malmqvist, P.-Å.; Roos, B. O.; Sadlej, A.; Wolinski, K. J. Phys. Chem. 1990, 94, 5483. (b) Anderson, K.; Malmqvist, P.-Å.; Roos, B. O. J. Chem. Phys. 1992, 96, 1218.
12. CASPT2N uses second-order, multi-reference perturbation theory to recover the correlation energy that is not recovered variationally in the active space. See: (a) Anderson, K.; Malmqvist, P.-Å.; Roos, B. O.; Sadlej, A.; Wolinski, K. J. Phys. Chem. 1990, 94, 5483. (b) Anderson, K.; Malmqvist, P.-Å.; Roos, B. O. J. Chem. Phys. 1992, 96, 1218.
13. Hariharan, P. C.; Pople, J. A. Theor. Chim. Acta 1973, 28, 213.
14. Gaussian 94, Revision B.3, Frisch, M. J.; Trucks, G. W.; Schlegel, H. B.; Gill, P. M. W.; Johnson, B. G.; Robb, M. A.; Cheeseman, J. R.; Keith, T.; Petersson, G. A.; Montgomery, J. A.; Raghavachari, K.; Al-Laham, M. A.; Zakrzewski, V. G.; Ortiz, J. V.; Foresman, J. B.; Peng, C. Y.; Ayala, P. Y.; Chen, W.; Wong, M. W.; Andres, J. L.; Replogle, E. S.; Gomperts, R.; Martin, R. L.; Fox, D. J.; Binkley, J. S.; Defrees, D. J.; Baker, J.; Stewart, J. P.; Head-Gordon, M.; Gonzalez, C.; and Pople, J. A.; Gaussian, Inc.: Pittsburgh, PA, 1995.
15. MOLCAS version 3, Anderson, K.; Blomberg, M. R. A.; Fülscher, M. P.; Kellö, V.; Lindh, R.; Malmqvist, P.-Å.; Noga, J.; Olsen, J.; Roos, B. O.; Sadlej, A. J.; Siegbahn, P. E. M.; Urban, M.; Widmark, P.-O.; University of Lund: Lund, Sweden, 1994.
16. Several different conformational isomers were optimized for each diradical. The structures for 6 and 7 that were of lowest energy at both the (2/2)CASSCF and (2/2)CASPT2N levels were each found to be a transition state by CASSCF vibrational analyses.
17. (a) Skancke, A.; Van Vechten, D.; Liebman, J. F.; Skancke, P. N. J. Mol. Struct. 1996, 376, 461.
18. (b) Boatz, J. A.; Gordon, M. S.; Hilderbrandt, R. L. J. Am. Chem. Soc. 1988, 110, 352
19. Anwari, F.; Gordon, M. S. Isr. J. Chem. 1983, 23, 129.
20. Gordon, M. S.; Truong, T. N. Chem. Phys. Lett. 1987, 142, 110.
21. MP2 for closed-shell species, UMP2 for radicals, and (2/2)-CASPT2N for silylenes and carbenes, uncorrected for ΔZPE.
22. In contrast, the C-H BDE of a primary vinyl radical in forming a singlet vinylidene is much less than the energy liberated in forming a C-H bond from a primary alkyl radical. It is for this reason that propenylidene was calculated to be lower in energy than propene-1,3-diyl (singlet vinylmethylene) and that cyclopropene was predicted to undergo ring opening to propenylidene by retograde, C-H insertion. [Yoshimine, M.; Pacansky, J.; Honjou, N. J. Am. Chem. Soc. 1989, 111, 4198 and references cited therein.] The prediction of ring opening of cyclopropene to propenylidene has subsequently been confirmed by several different experiments. [(a) Walsh, R.; Wolf, C.; Untiedt, S.; de Meijere, A. J. Chem. Soc., Chem. Commun. 1992, 421. (b) Hopf, H.; Plagens, A.; Walsh, R. J. Chem. Soc., Chem. Commun. 1994, 1467. (c) Likhotvorik, I. R.; Brown, D. W.; Jones, M., Jr. J. Am. Chem. Soc. 1994, 116, 6175. (d) Hopf, H.; Graf von der Schulenberg, W.; Walsh, R. Angew. Chem., Int. Ed. Engl. 1997, 36, 381.]
23. In contrast, the C-H BDE of a primary vinyl radical in forming a singlet vinylidene is much less than the energy liberated in forming a C-H bond from a primary alkyl radical. It is for this reason that propenylidene was calculated to be lower in energy than propene-1,3-diyl (singlet vinylmethylene) and that cyclopropene was predicted to undergo ring opening to propenylidene by retograde, C-H insertion. [Yoshimine, M.; Pacansky, J.; Honjou, N. J. Am. Chem. Soc. 1989, 111, 4198 and references cited therein.] The prediction of ring opening of cyclopropene to propenylidene has subsequently been confirmed by several different experiments. [(a) Walsh, R.; Wolf, C.; Untiedt, S.; de Meijere, A. J. Chem. Soc., Chem. Commun. 1992, 421. (b) Hopf, H.; Plagens, A.; Walsh, R. J. Chem. Soc., Chem. Commun. 1994, 1467. (c) Likhotvorik, I. R.; Brown, D. W.; Jones, M., Jr. J. Am. Chem. Soc. 1994, 116, 6175. (d) Hopf, H.; Graf von der Schulenberg, W.; Walsh, R. Angew. Chem., Int. Ed. Engl. 1997, 36, 381.]
24. In contrast, the C-H BDE of a primary vinyl radical in forming a singlet vinylidene is much less than the energy liberated in forming a C-H bond from a primary alkyl radical. It is for this reason that propenylidene was calculated to be lower in energy than propene-1,3-diyl (singlet vinylmethylene) and that cyclopropene was predicted to undergo ring opening to propenylidene by retograde, C-H insertion. [Yoshimine, M.; Pacansky, J.; Honjou, N. J. Am. Chem. Soc. 1989, 111, 4198 and references cited therein.] The prediction of ring opening of cyclopropene to propenylidene has subsequently been confirmed by several different experiments. [(a) Walsh, R.; Wolf, C.; Untiedt, S.; de Meijere, A. J. Chem. Soc., Chem. Commun. 1992, 421. (b) Hopf, H.; Plagens, A.; Walsh, R. J. Chem. Soc., Chem. Commun. 1994, 1467. (c) Likhotvorik, I. R.; Brown, D. W.; Jones, M., Jr. J. Am. Chem. Soc. 1994, 116, 6175. (d) Hopf, H.; Graf von der Schulenberg, W.; Walsh, R. Angew. Chem., Int. Ed. Engl. 1997, 36, 381.]
25. In contrast, the C-H BDE of a primary vinyl radical in forming a singlet vinylidene is much less than the energy liberated in forming a C-H bond from a primary alkyl radical. It is for this reason that propenylidene was calculated to be lower in energy than propene-1,3-diyl (singlet vinylmethylene) and that cyclopropene was predicted to undergo ring opening to propenylidene by retograde, C-H insertion. [Yoshimine, M.; Pacansky, J.; Honjou, N. J. Am. Chem. Soc. 1989, 111, 4198 and references cited therein.] The prediction of ring opening of cyclopropene to propenylidene has subsequently been confirmed by several different experiments. [(a) Walsh, R.; Wolf, C.; Untiedt, S.; de Meijere, A. J. Chem. Soc., Chem. Commun. 1992, 421. (b) Hopf, H.; Plagens, A.; Walsh, R. J. Chem. Soc., Chem. Commun. 1994, 1467. (c) Likhotvorik, I. R.; Brown, D. W.; Jones, M., Jr. J. Am. Chem. Soc. 1994, 116, 6175. (d) Hopf, H.; Graf von der Schulenberg, W.; Walsh, R. Angew. Chem., Int. Ed. Engl. 1997, 36, 381.]
26. In contrast, the C-H BDE of a primary vinyl radical in forming a singlet vinylidene is much less than the energy liberated in forming a C-H bond from a primary alkyl radical. It is for this reason that propenylidene was calculated to be lower in energy than propene-1,3-diyl (singlet vinylmethylene) and that cyclopropene was predicted to undergo ring opening to propenylidene by retograde, C-H insertion. [Yoshimine, M.; Pacansky, J.; Honjou, N. J. Am. Chem. Soc. 1989, 111, 4198 and references cited therein.] The prediction of ring opening of cyclopropene to propenylidene has subsequently been confirmed by several different experiments. [(a) Walsh, R.; Wolf, C.; Untiedt, S.; de Meijere, A. J. Chem. Soc., Chem. Commun. 1992, 421. (b) Hopf, H.; Plagens, A.; Walsh, R. J. Chem. Soc., Chem. Commun. 1994, 1467. (c) Likhotvorik, I. R.; Brown, D. W.; Jones, M., Jr. J. Am. Chem. Soc. 1994, 116, 6175. (d) Hopf, H.; Graf von der Schulenberg, W.; Walsh, R. Angew. Chem., Int. Ed. Engl. 1997, 36, 381.]
27. Without correcting for zero-point energies, CASPT2N finds 15 kcal/ mol for this difference in C-H versus Si-H BDEs.
28. Parmar, S. S.; Benson, S. W. J. Am. Chem. Soc. 1989, 111, 57.
29. Walsh, R. Acc. Chem. Res. 1981, 14, 246.
30. The different spatial extents of 3s and 3p orbitals result in unshared electrons on atoms in the second row of the periodic table generally occupying AO's with much more s character than unshared electrons on atoms in the first row. Kutzelnigg, W. Angew. Chem., Int. Ed. Engl. 1984, 23, 272.