Ligand transfer selectivity in the conjugate addition of a mixed organocuprate bearing a dummy ligand [1]

Journal of the American Chemical Society

Volumn 121, Issue 38, 1999, Pages 8941-8942

  Nakamura, Eiichi ^a   Yamanaka, Asahiro ^a  

^a UNIVERSITY OF TOKYO   (Japan)

Author keywords

[No Author keywords available]

Indexed keywords

LIGAND;

CHEMICAL REACTION; CHEMICAL STRUCTURE; LETTER; LIGAND BINDING; SYNTHESIS;

EID: 0033615302     PISSN: 00027863     EISSN: None     Source Type: Journal    
DOI: 10.1021/ja991324u     Document Type: Letter

References (31)

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9. The basis set denoted as 631A consists of Ahlrichs all-electron SVP basis set for the Cu atom and 6-31G(d) for the rest. For details of theoretical methods and chemical models of cuprate clusters, see: Nakamura, E.; Mori, S.; Nakamura, M.; Morokuma, K. J. Am. Chem. Soc. 1997, 119, 4887-4899. Mori, S.; Nakamura, E. J. Mol. Struct. (THEOCHEM) 1999, 461-462, 167- 175.
10. The basis set denoted as 631A consists of Ahlrichs all-electron SVP basis set for the Cu atom and 6-31G(d) for the rest. For details of theoretical methods and chemical models of cuprate clusters, see: Nakamura, E.; Mori, S.; Nakamura, M.; Morokuma, K. J. Am. Chem. Soc. 1997, 119, 4887-4899. Mori, S.; Nakamura, E. J. Mol. Struct. (THEOCHEM) 1999, 461-462, 167-175.
11. Frantz, D. E.; Singleton, D. A.; Snyder, J. P. J. Am. Chem. Soc. 1997, 119, 3383-3384.
12. (a) Nakamura, E.; Mori, S.; Morokuma, K. J. Am. Chem. Soc. 1997, 119, 4900-4910.
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17. - shows the same trend (X = Me, 1.97 Å; ethynyl, 1.90 Å; cyano, 1.91 Å).
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19. (a) Boys, S. F. Quantum Theory of Atoms, Molecules, and the Solid State; Lowdin, P. O., Ed.; Academic Press: New York, 1968; pp 253-262. Haddon, R. C.; Williams, G. R. J. Chem. Phys. Lett. 1976, 42, 453-455.
20. (b) Kohn, W.; Sham, L. J. Phys. Rev. 1965, 140, A1133-1138.
21. The energy comparison is made here for CPxm and CPmx, which are in mobile equilibrium with each other. Therefore Curtin-Hammet boundary conditions are satisfied (see ref 4b), and one needs to consider only the energies of the TSs for the analysis of ligand transfer selectivity. The energy of the reactants serves only as a reference zero point.
22. Such consideration also accounts for the low reactivities of bis(alkynyl) homocuprates in terms of the thermodynamic problem in dissociation of the Li-X bond in the starting cuprate cluster.
23. (a) Goldfuss, B.; Schleyer, P. v. R.; Hampel, F. J. Am. Chem. Soc. 1997. 119, 1072.
24. (b) Varga, V.; Mach, K.; Thewalt, H. U. J. Organomet. Chem. 1996, 506, 109.
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26. Cf.: Hirai, A.; Nakamura, M.; Nakamura, E. J. Am. Chem. Soc. accepted for publication. Nakamura, E.; Hirai, A.; Nakamura, M. J. Am. Chem. Soc. 1998, 120, 5844-5845. Nakamura, M.; Nakamura, E.; Koga, N.; Morokuma, K. J. Am. Chem. Soc. 1993, 115, 11016-11017. Nakamura, M.; Nakamura, E.; Koga, N.; Morokuma, K. J. Chem. Soc., Faraday Trans. 1994, 90, 1789-1798. Mori, S.; Kim, B. H.; Nakamura, M.; Nakamura, E. Chem. Lett. 1997, 1079-1080.
27. Cf.: Hirai, A.; Nakamura, M.; Nakamura, E. J. Am. Chem. Soc. accepted for publication. Nakamura, E.; Hirai, A.; Nakamura, M. J. Am. Chem. Soc. 1998, 120, 5844-5845. Nakamura, M.; Nakamura, E.; Koga, N.; Morokuma, K. J. Am. Chem. Soc. 1993, 115, 11016-11017. Nakamura, M.; Nakamura, E.; Koga, N.; Morokuma, K. J. Chem. Soc., Faraday Trans. 1994, 90, 1789-1798. Mori, S.; Kim, B. H.; Nakamura, M.; Nakamura, E. Chem. Lett. 1997, 1079-1080.
28. Cf.: Hirai, A.; Nakamura, M.; Nakamura, E. J. Am. Chem. Soc. accepted for publication. Nakamura, E.; Hirai, A.; Nakamura, M. J. Am. Chem. Soc. 1998, 120, 5844-5845. Nakamura, M.; Nakamura, E.; Koga, N.; Morokuma, K. J. Am. Chem. Soc. 1993, 115, 11016-11017. Nakamura, M.; Nakamura, E.; Koga, N.; Morokuma, K. J. Chem. Soc., Faraday Trans. 1994, 90, 1789-1798. Mori, S.; Kim, B. H.; Nakamura, M.; Nakamura, E. Chem. Lett. 1997, 1079-1080.
29. Cf.: Hirai, A.; Nakamura, M.; Nakamura, E. J. Am. Chem. Soc. accepted for publication. Nakamura, E.; Hirai, A.; Nakamura, M. J. Am. Chem. Soc. 1998, 120, 5844-5845. Nakamura, M.; Nakamura, E.; Koga, N.; Morokuma, K. J. Am. Chem. Soc. 1993, 115, 11016-11017. Nakamura, M.; Nakamura, E.; Koga, N.; Morokuma, K. J. Chem. Soc., Faraday Trans. 1994, 90, 1789-1798. Mori, S.; Kim, B. H.; Nakamura, M.; Nakamura, E. Chem. Lett. 1997, 1079-1080.
30. Cf.: Hirai, A.; Nakamura, M.; Nakamura, E. J. Am. Chem. Soc. accepted for publication. Nakamura, E.; Hirai, A.; Nakamura, M. J. Am. Chem. Soc. 1998, 120, 5844-5845. Nakamura, M.; Nakamura, E.; Koga, N.; Morokuma, K. J. Am. Chem. Soc. 1993, 115, 11016-11017. Nakamura, M.; Nakamura, E.; Koga, N.; Morokuma, K. J. Chem. Soc., Faraday Trans. 1994, 90, 1789-1798. Mori, S.; Kim, B. H.; Nakamura, M.; Nakamura, E. Chem. Lett. 1997, 1079-1080.
31. 3D pictures and coordinates are available on http://www.chem.s.u-tokyo.ac.jp/~common/Theo/Mixl/title.