Disrotatory and conrotatory transition structures for the Fe(CO)3-templated rearrangement of methylenecyclopropane to trimethylenemethane

Organometallics

Volumn 20, Issue 22, 2001, Pages 4562-4564

  Tantillo, Dean J ^a   Carpenter, Barry K ^a   Hoffmann, Roald ^a  

^a Department of Obstetrics Gynecology   (United States)

Author keywords

[No Author keywords available]

Indexed keywords

IRON CARBONATE; METHYLENECYCLOPROPANE; TRIMETHYLENEMETHANE;

ADDITION REACTIONS; CARRIER CONCENTRATION; COMPLEXATION; CRYSTAL SYMMETRY; ELECTRON ENERGY LEVELS; IRON COMPOUNDS; MOLECULAR STRUCTURE; NUMERICAL ANALYSIS; PERTURBATION TECHNIQUES; PHASE TRANSITIONS; PROBABILITY DENSITY FUNCTION;

ORGANOMETALLICS;

EID: 0035969282     PISSN: 02767333     EISSN: None     Source Type: Journal    
DOI: 10.1021/om010579p     Document Type: Article

References (27)

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5. 3-methylenecyclopropane complexes. See ref 1c for details.
6. This selectivity for a particular sense of disrotatory ring-opening is related to the torquoselectivity predicted and observed previously for uncomplexed conrotatory ring-openings of substituted cyclobutenes: Dolbier, W. R. Jr.; Koroniak, H.; Houk, K. N.; Sheu, C. Acc. Chem. Res. 1996, 29, 471-477.
7. Frisch, M. J.; Trucks, G. W.; Schlegel, H. B.; Scuseria, G. E.; Robb, M. A.; Cheeseman, J. R.; Zakrzewski, V. G.; Montgomery, J. A., Jr.; Stratmann, R. E.; Burant, J. C.; Dapprich, S.; Millam, J. M.; Daniels, A. D.; Kudin, K. N.; Strain, M. C.; Farkas, O.; Tomasi, J.; Barone, V.; Cossi, M.; Cammi, R.; Mennucci, B.; Pomelli, C.; Adamo, C.; Clifford, S.; Ochterski, J.; Petersson, G. A.; Ayala, P. Y.; Cui, Q.; Morokuma, K.; Malick, D. K.; Rabuck, A. D.; Raghavachari, K.; Foresman, J. B.; Cioslowski, J.; Ortiz, J. V.; Stefanov, B. B.; Liu, G.; Liashenko, A.; Piskorz, P.; Komaromi, I. R.; Gomperts, R.; Martin, L.; Fox, D. J.; Keith, T.; Al-Laham, M. A.; Peng, C. Y.; Nanayakkara, A.; Gonzalez, C.; Challacombe, M. P.; Gill, M. W.; Johnson, B.; Chen, W.; Wong, M. W.; Andres, J. L.; Gonzalez, C.; Head-Gordon, M.; Replogle, E. S.; Pople, J. A. GAUSSIAN 98; Gaussian, Inc.: Pittsburgh, PA, 1998; Revision A. 9.
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13. The DZVP2 basis set was obtained from the Extensible Computational Chemistry Environment Basis Set Database, Version 1.0 (http://www.emsl.pnl.gov:2080/forms/basisform.html), as develop and distributed by the Molecular Science Computing Facility, Environmental and Molecular Sciences Laboratory, which is part of the Pacific Northwest Laboratory, P.O. Box 999, Richland, WA 99352, and funded by the U.S. Department of Energy (contract DE-AC06-76RLO 1830). Contact David Feller, Karen Schuchardt, or Don Jones for further information. The original DZVP2 basis set (Godbout, N.; Salahub, D. R.; Andzelm, J.; Wimmer, E. Can. J. Chem. 1992, 70, 560-571)
14. was augmented as described in: Braden, D. A.; Tyler, D. R. J. Am. Chem. Soc. 1998, 120, 942-947.
15. Recent applications of this methodology include: (a) Merlic, C. A.; Walsh, J. C.; Tantillo, D. J.; Houk, K. N. J. Am. Chem. Soc. 1999, 121, 3596-3606.
16. (b) Tantillo, D. J.; Hietbrink, B. N.; Merlic, C. A.; Houk, K. N. J. Am. Chem. Soc. 2000, 122, 7136-1737.
17. (additional note: Tantillo, D. J.; Hietbrink, B. N.; Merlic, C. A.; Houk, K. N. J. Am. Chem. Soc. 2001, 123, 5851).
18. (c) Creary, X. Org. Lett. 2000, 2, 2069-2072.
19. For recent reviews on DFT applied to transition metals, including comparisons with more expensive multiconfigurational methods, see: (a) Niu, S.; Hall, M. B. Chem. Rev. 2000, 100, 353-406.
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21. (c) Koch, W.; Hartwig, R. H. In The Encyclopedia of Computational Chemistry; Schleyer, P. v. R., Allinger, N. L., Clark, T., Gasteiger, J., Kollman, P. A., Schaeffer, H. F., III., Schreiner, P. R., Eds.; John Wiley & Sons: Chichester, 1998; p 689.
22. Lewis, S. B.; Hrovat, D. A.; Getty, S. J.; Borden, W. T. J. Chem. Soc., Perkin Trans. 1999, 2, 2339-2347, and references therein.
23. 2> values for assessing spin contamination in DFT calculations is still in debate; Gräfenstein, J.; Cremer, D. Mol. Phys. 2001, 99, 981-989.) Although this level of theory appears to be inadequate for accurate descriptions of teh diradical species involved in the uncomplexed ring-opening, the metal-complexed reactions do not involve such species, and this level of theory has been shown to be appropriate for characterizing related closed-shell species.
24. C-C and Fe-C distances in 9 are in excellent agreement with analogoues distances computed by Koch and co-workers for a methylated derivative of 9 using an all-electron basis set for optimization. Their C-C distances are all 1.44 Å, and their Fe-C distances range from 1.96 to 2.17 Å. Pfletschinger, A.; Schmalz, H.-G.; Koch, W. Eur. J. Inorg. Chem. 1999, 1869-1880.
25. Graphical depictions of structures were produced using: Müller, N.; Falk, A. Ball & Stick 3.7.6, a molecular graphics application for MacOS computers; Johannes Kepler University: Linz, 2000.
26. s symmetry.
27. Tantillo, D. J.; Hoffmann, R. Helv. Chem. Acta 2001, 84, 1396-1404.