Correlation of coordination geometry of copper atom to reactivities of organocuprate. Molecular orbital analysis of dimethylcuprate anion

Tetrahedron Letters

Volumn 40, Issue 29, 1999, Pages 5319-5322

  Mori, Seiji ^a,b   Nakamura, Eiichi ^a  

^a UNIVERSITY OF TOKYO   (Japan)

^b EMORY UNIVERSITY   (United States)

Author keywords

Carbocupration; Conjugate addition; Density functional theory; Mechanism; Organocuprate

Indexed keywords

ACETYLENE; ALKENE; CARBOXYLIC ACID; COPPER; COPPER DERIVATIVE;

ALKYLATION; ARTICLE; ATOM; CHEMICAL STRUCTURE; CHEMOREACTIVITY; CONFORMATION; CRYSTAL STRUCTURE; GEOMETRY;

EID: 0033575460     PISSN: 00404039     EISSN: None     Source Type: Journal    
DOI: 10.1016/S0040-4039(99)00966-1     Document Type: Article

References (32)

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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, and the set denoted as 6311A consists of Ahlrichs DZP all-electron basis set for copper and 6-311+G(d,p) for the rest. See: Schäfer, A.; Horn, H.; Ahlrichs, R. J. Chem. Phys. 1992, 97, 2571. Hehre, W. J.; Radom, L.; Schleyer, P. v. R.; Pople, J. A.Ab Initio Molecular Orbital Theory, John Wiley: New York, 1986. See ref 9a for details.
11. 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, and the set denoted as 6311A consists of Ahlrichs DZP all-electron basis set for copper and 6-311+G(d,p) for the rest. See: Schäfer, A.; Horn, H.; Ahlrichs, R. J. Chem. Phys. 1992, 97, 2571. Hehre, W. J.; Radom, L.; Schleyer, P. v. R.; Pople, J. A. Ab Initio Molecular Orbital Theory, John Wiley: New York, 1986. See ref 9a for details.
12. (a) Nakamura, E.; Mori, S.; Nakamura, M.; Morokuma, K. J. Am. Chem. Soc. 1997, 119, 4887-4899. 3D pictures and coordinates: http://www.chem.s.u-tokyo.ac.jp/~common/Theo/Cb/title. (b) Mori, S.; Nakamura, E. Theochem (Morokuma special Issue), 1999, 461-462, 167-175.
13. (a) Nakamura, E.; Mori, S.; Nakamura, M.; Morokuma, K. J. Am. Chem. Soc. 1997, 119, 4887-4899. 3D pictures and coordinates: http://www.chem.s.u-tokyo.ac.jp/~common/Theo/Cb/title. (b) Mori, S.; Nakamura, E. Theochem (Morokuma special Issue), 1999, 461-462, 167-175.
14. Nakamura, E.; Mori, S.; Morokuma, K. J. Am. Chem. Soc. 1997, 119, 4900-4910 3D pictures and coordinates: http://www.chem.s.u-tokyo.ac.jp/~common/Theo/Cj1/title). Mori, S. Nakamura, E. Chem. Eur. J. 1999, 5, 1534-1543 (3D pictures and coordinates: http://www.chem.s.u-tokyo.ac.jp/~common/Theo/Cj2/title).
15. Nakamura, E.; Mori, S.; Morokuma, K. J. Am. Chem. Soc. 1997, 119, 4900-4910 3D pictures and coordinates: http://www.chem.s.u-tokyo.ac.jp/~common/Theo/Cj1/title). Mori, S. Nakamura, E. Chem. Eur. J. 1999, 5, 1534-1543 (3D pictures and coordinates: http://www.chem.s.u-tokyo.ac.jp/~common/Theo/Cj2/title).
16. Nakamura, E.; Mori, S.; Morokuma, K. J. Am. Chem. Soc. 1998, 120 8273-8274 (3D pictures and coordinates: http://www.chem.s.u-tokyo.ac.jp/~common/Theo/Sn1/title).
17. Cf. Burdett, J. K. Molecular Shapes, Wiley, New York, 1980.
18. 2 orbital which consists of methyl s+p orbitals (B3LYP/6-311+G**-SKBJ//B3LYP/6-31G*-SKBJ). For the SKBJ Effective Core Potential for Au, See: Stevens, W. J.; Krauss, M.; Basch, H.; Jasien, P. G. Can. J. Chem. 1992, 70, 612-630.
19. 2CuLi·LiCl/acetylene Complex (CP in eq 1 and Ref 9a).
20. 3-Cu bond consists of 83% carbon electrons (s+p orbitals) and 17% copper electrons (85% s + 15% d). Boys, S. F. Quantum Theory of Atoms, Molecules, and the Solid State; (Ed.: P. O. Lowdin) Academic Press: New York, USA, 1968, pp.253-262. NBO 4.0. Glendening, E. D.; Badenhoop, J. K.; Reed, A. E.; Carpenter, J. E.; Weinhold, F. Theoretical Chemistry, Institute, University of Wisconsin, Madison, WI, 1996. For literature on the nature of C-Cu bonds, see: Antes, I.; Frenking, G. Organometallics, 1995, 14, 4263-4268.
21. 3-Cu bond consists of 83% carbon electrons (s+porbitals) and 17% copper electrons (85% s + 15% d). Boys, S. F. Quantum Theory of Atoms, Molecules, and the Solidstate; (Ed.: P. O. Lowdin) Academic Press: New York, USA, 1968, pp.253-262. NBO 4.0. Glendening, E. D.; Badenhoop, J. K.; Reed, A. E.; Carpenter, J. E.; Weinhold, F. Theoretical Chemistry, Institute, University of Wisconsin, Madison, WI, 1996. For literature on the nature of C-Cu bonds, see: Antes, I.; Frenking, G. Organometallics, 1995, 14, 4263-4268.
22. 3-Cu bond consists of 83% carbon electrons (s+porbitals) and 17% copper electrons (85% s + 15% d). Boys, S. F. Quantum Theory of Atoms, Molecules, and the Solidstate; (Ed.: P. O. Lowdin) Academic Press: New York, USA, 1968, pp.253-262. NBO 4.0. Glendening, E. D.; Badenhoop, J. K.; Reed, A. E.; Carpenter, J. E.; Weinhold, F. Theoretical Chemistry, Institute, University of Wisconsin, Madison, WI, 1996. For literature on the nature of C-Cu bonds, see: Antes, I.; Frenking, G. Organometallics, 1995, 14, 4263-4268.
23. Albright, T. A.; Hoffmann, R.; Thibeault, J. C.; Thorn, D. L.; J. Am. Chem. Soc. 1979, 101, 3801-3812. Dedieu, A.; Hoffmann, R. J. Am. Chem. Soc. 1978, 100, 2074-2079.
24. Albright, T. A.; Hoffmann, R.; Thibeault, J. C.; Thorn, D. L.; J. Am. Chem. Soc. 1979, 101, 3801-3812. Dedieu, A.; Hoffmann, R. J. Am. Chem. Soc. 1978, 100, 2074-2079.
25. Cf.: Galbraith, J. M.; Schaefer III, H. F. J. Chem. Phys. 1996, 105, 862.
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27. Bickelhaupt, F. M.; Ziegler, T.; Schleyer, P. V. R. Organometallics 1995, 14, 2288-2296.
28. For the equal importance of high-lying molecular orbitals in the FMO interactions, see: Fujimoto, H. Acc. Chem. Res. 1987, 20, 448-453.
29. For earlier discussions on d-orbital participation in the cuprate/olefin interaction, see Corey, E. J.; Boaz, N. W. Tetrahedron Lett. 1984, 25, 3063-3066.
30. Activation barrier of Gibbs free energy from reactants to TS is kcal/mol at °C and 1 atm at the B3LYP/631A level.
31. Cf. Bickelhaupt, F. M. J. Comput. Chem. 1999, 20, 114-128; Kaupp, M. J. Am. Chem. Soc. 1996, 118, 3018-3024.
32. Cf. Bickelhaupt, F. M. J. Comput. Chem. 1999, 20, 114-128; Kaupp, M. J. Am. Chem. Soc. 1996, 118, 3018-3024.