Ab initio theoretical study of the reactivity as bases or nucleophiles of potassium and lithium methides

Journal of Physical Organic Chemistry

Volumn 10, Issue 12, 1997, Pages 885-897

  Ghigo, Giovanni ^a   Tonachini, Glauco ^a   Fossey, Jacques ^b  

^a UNIVERSITY OF TURIN   (Italy)

^b LABORATOIRE HÉTÉROÉLÉMENTS ET COORDINATION   (France)

Author keywords

Ab initia studies; Potassium and lithium methods; Reactivity

Indexed keywords

EID: 0000805498     PISSN: 08943230     EISSN: None     Source Type: Journal    
DOI: 10.1002/(SICI)1099-1395(199712)10:12<885::AID-POC955>3.0.CO;2-5     Document Type: Article

References (39)

1. (a) Effective substituents are, for instance, second-row elements such as sulfur, carbonyl or cyano groups or other conjugated multiple bonds (Michael-type reactions). Also alkenes with an electron donor group in a suitable position (such as allylic alcohol, see below): equation presented have been reported to undergo readily addition of organolithiums. See: B. J. Wakefield, in Organolithium Methods, Chap. 4. Academic Press, New York (1990); (b) H. E. Podall and W. E. Foster, J. Org. Chem. 23, 1848-1852 (1958); (c) J. K. Crandall and A. J. Rojas, Org. Synth. 55, 1-3 (1976); (d) M. Nakamura, E. Nakamura, N. Koga and K. Morokuma, J. Chem. Soc., Faraday Trans. 90, 1789-1798 (1994); E. Nakamura, M. Nakamura, Y. Miyachi, N. Koga and K. Morokuma, J. Am. Chem. Soc. 115, 99-106 (1993); E. Nakamura, Y. Miyachi, N. Koga and K. Morokuma, J. Am. Chem. Soc. 114, 6686-6692 (1992).
2. (a) Effective substituents are, for instance, second-row elements such as sulfur, carbonyl or cyano groups or other conjugated multiple bonds (Michael-type reactions). Also alkenes with an electron donor group in a suitable position (such as allylic alcohol, see below): equation presented have been reported to undergo readily addition of organolithiums. See: B. J. Wakefield, in Organolithium Methods, Chap. 4. Academic Press, New York (1990); (b) H. E. Podall and W. E. Foster, J. Org. Chem. 23, 1848-1852 (1958); (c) J. K. Crandall and A. J. Rojas, Org. Synth. 55, 1-3 (1976); (d) M. Nakamura, E. Nakamura, N. Koga and K. Morokuma, J. Chem. Soc., Faraday Trans. 90, 1789-1798 (1994); E. Nakamura, M. Nakamura, Y. Miyachi, N. Koga and K. Morokuma, J. Am. Chem. Soc. 115, 99-106 (1993); E. Nakamura, Y. Miyachi, N. Koga and K. Morokuma, J. Am. Chem. Soc. 114, 6686-6692 (1992).
3. (a) Effective substituents are, for instance, second-row elements such as sulfur, carbonyl or cyano groups or other conjugated multiple bonds (Michael-type reactions). Also alkenes with an electron donor group in a suitable position (such as allylic alcohol, see below): equation presented have been reported to undergo readily addition of organolithiums. See: B. J. Wakefield, in Organolithium Methods, Chap. 4. Academic Press, New York (1990); (b) H. E. Podall and W. E. Foster, J. Org. Chem. 23, 1848-1852 (1958); (c) J. K. Crandall and A. J. Rojas, Org. Synth. 55, 1-3 (1976); (d) M. Nakamura, E. Nakamura, N. Koga and K. Morokuma, J. Chem. Soc., Faraday Trans. 90, 1789-1798 (1994); E. Nakamura, M. Nakamura, Y. Miyachi, N. Koga and K. Morokuma, J. Am. Chem. Soc. 115, 99-106 (1993); E. Nakamura, Y. Miyachi, N. Koga and K. Morokuma, J. Am. Chem. Soc. 114, 6686-6692 (1992).
4. (a) Effective substituents are, for instance, second-row elements such as sulfur, carbonyl or cyano groups or other conjugated multiple bonds (Michael-type reactions). Also alkenes with an electron donor group in a suitable position (such as allylic alcohol, see below): equation presented have been reported to undergo readily addition of organolithiums. See: B. J. Wakefield, in Organolithium Methods, Chap. 4. Academic Press, New York (1990); (b) H. E. Podall and W. E. Foster, J. Org. Chem. 23, 1848-1852 (1958); (c) J. K. Crandall and A. J. Rojas, Org. Synth. 55, 1-3 (1976); (d) M. Nakamura, E. Nakamura, N. Koga and K. Morokuma, J. Chem. Soc., Faraday Trans. 90, 1789-1798 (1994); E. Nakamura, M. Nakamura, Y. Miyachi, N. Koga and K. Morokuma, J. Am. Chem. Soc. 115, 99-106 (1993); E. Nakamura, Y. Miyachi, N. Koga and K. Morokuma, J. Am. Chem. Soc. 114, 6686-6692 (1992).
5. (a) Effective substituents are, for instance, second-row elements such as sulfur, carbonyl or cyano groups or other conjugated multiple bonds (Michael-type reactions). Also alkenes with an electron donor group in a suitable position (such as allylic alcohol, see below): equation presented have been reported to undergo readily addition of organolithiums. See: B. J. Wakefield, in Organolithium Methods, Chap. 4. Academic Press, New York (1990); (b) H. E. Podall and W. E. Foster, J. Org. Chem. 23, 1848-1852 (1958); (c) J. K. Crandall and A. J. Rojas, Org. Synth. 55, 1-3 (1976); (d) M. Nakamura, E. Nakamura, N. Koga and K. Morokuma, J. Chem. Soc., Faraday Trans. 90, 1789-1798 (1994); E. Nakamura, M. Nakamura, Y. Miyachi, N. Koga and K. Morokuma, J. Am. Chem. Soc. 115, 99-106 (1993); E. Nakamura, Y. Miyachi, N. Koga and K. Morokuma, J. Am. Chem. Soc. 114, 6686-6692 (1992).
6. (a) Effective substituents are, for instance, second-row elements such as sulfur, carbonyl or cyano groups or other conjugated multiple bonds (Michael-type reactions). Also alkenes with an electron donor group in a suitable position (such as allylic alcohol, see below): equation presented have been reported to undergo readily addition of organolithiums. See: B. J. Wakefield, in Organolithium Methods, Chap. 4. Academic Press, New York (1990); (b) H. E. Podall and W. E. Foster, J. Org. Chem. 23, 1848-1852 (1958); (c) J. K. Crandall and A. J. Rojas, Org. Synth. 55, 1-3 (1976); (d) M. Nakamura, E. Nakamura, N. Koga and K. Morokuma, J. Chem. Soc., Faraday Trans. 90, 1789-1798 (1994); E. Nakamura, M. Nakamura, Y. Miyachi, N. Koga and K. Morokuma, J. Am. Chem. Soc. 115, 99-106 (1993); E. Nakamura, Y. Miyachi, N. Koga and K. Morokuma, J. Am. Chem. Soc. 114, 6686-6692 (1992).
7. - distance of ca 3-02 Å, instead of the more usual 2.88-2.89 Å; G. Ghigo, G. Tonachini and P. Venturello, Tetrahedron 52, 7053-7062 (1996).
8. - distance of ca 3-02 Å, instead of the more usual 2.88-2.89 Å; G. Ghigo, G. Tonachini and P. Venturello, Tetrahedron 52, 7053-7062 (1996).
9. - distance of ca 3-02 Å, instead of the more usual 2.88-2.89 Å; G. Ghigo, G. Tonachini and P. Venturello, Tetrahedron 52, 7053-7062 (1996).
10. - distance of ca 3-02 Å, instead of the more usual 2.88-2.89 Å; G. Ghigo, G. Tonachini and P. Venturello, Tetrahedron 52, 7053-7062 (1996).
11. A pK of ca 43 is estimated for propene in LiCHA-CHA: D. W. Boerth and A. Streitwieser, Jr, J. Am. Chem. Soc. 103, 6443-6447 (1981); a value ranging from 47 to 48 in THF-HMPA was also estimated: B. Jaun, J. Schwarz and R. Breslow, J. Am. Chem. Soc. 102, 5741-5748 (1980). The pK value for methane was extrapolated from toluene and diphenylmethane: the estimate ranges from 52 to 62 (same reference). For a discussion on the acidity of hydrocarbons see, for instance: F. A. Carey and R. J. Sundberg, Advanced Organic Chemistry, Chapt. 7. Plenum Press, New York, (1990).
12. A pK of ca 43 is estimated for propene in LiCHA-CHA: D. W. Boerth and A. Streitwieser, Jr, J. Am. Chem. Soc. 103, 6443-6447 (1981); a value ranging from 47 to 48 in THF-HMPA was also estimated: B. Jaun, J. Schwarz and R. Breslow, J. Am. Chem. Soc. 102, 5741-5748 (1980). The pK value for methane was extrapolated from toluene and diphenylmethane: the estimate ranges from 52 to 62 (same reference). For a discussion on the acidity of hydrocarbons see, for instance: F. A. Carey and R. J. Sundberg, Advanced Organic Chemistry, Chapt. 7. Plenum Press, New York, (1990).
13. A pK of ca 43 is estimated for propene in LiCHA-CHA: D. W. Boerth and A. Streitwieser, Jr, J. Am. Chem. Soc. 103, 6443-6447 (1981); a value ranging from 47 to 48 in THF-HMPA was also estimated: B. Jaun, J. Schwarz and R. Breslow, J. Am. Chem. Soc. 102, 5741-5748 (1980). The pK value for methane was extrapolated from toluene and diphenylmethane: the estimate ranges from 52 to 62 (same reference). For a discussion on the acidity of hydrocarbons see, for instance: F. A. Carey and R. J. Sundberg, Advanced Organic Chemistry, Chapt. 7. Plenum Press, New York, (1990).
14. For the oligomerìzation of alkyllithiums, see: E. Kaufmann, J. Gose and P. v. R. Schleyer, Organometallics 8, 2577-2584 (1989); E. Kaufmann, K. Raghavachari, A. E. Reed and P. v. R. Schleyer, Organometallics 7, 1597-1607 (1988), and references cited therein. Here MeLi is just considered as a simple model for a generic alkyl group, and aggregation problems are plainly neglected. Not all alkyllithium have a strong inclination to aggregate: bulky t-BuLi. for instance, has been shown to exist as a monomer in tetrahydrofuran: W. Bauer, W. R. Winchester and P. v. R. Schleyer, Organometallics 6, 2371-2379 (1987). Theoretical studies carried out in this laboratory indicate that changing the structure of the anionic moiety by introduction of heteroatoms (Y) significantly affects the anion - cation interactions which determine the tendency to give aggregates; see, for Y=F, C. Canepa, P. Antoniotti and G. Tonachini, Tetrahedron 50, 8073-8084 (1994), and, for Y=Cl, C. Canepa and G. Tonachini, Tetrahedron 50, 12511-12520 (1994).
15. For the oligomerìzation of alkyllithiums, see: E. Kaufmann, J. Gose and P. v. R. Schleyer, Organometallics 8, 2577-2584 (1989); E. Kaufmann, K. Raghavachari, A. E. Reed and P. v. R. Schleyer, Organometallics 7, 1597-1607 (1988), and references cited therein. Here MeLi is just considered as a simple model for a generic alkyl group, and aggregation problems are plainly neglected. Not all alkyllithium have a strong inclination to aggregate: bulky t-BuLi. for instance, has been shown to exist as a monomer in tetrahydrofuran: W. Bauer, W. R. Winchester and P. v. R. Schleyer, Organometallics 6, 2371-2379 (1987). Theoretical studies carried out in this laboratory indicate that changing the structure of the anionic moiety by introduction of heteroatoms (Y) significantly affects the anion - cation interactions which determine the tendency to give aggregates; see, for Y=F, C. Canepa, P. Antoniotti and G. Tonachini, Tetrahedron 50, 8073-8084 (1994), and, for Y=Cl, C. Canepa and G. Tonachini, Tetrahedron 50, 12511-12520 (1994).
16. For the oligomerìzation of alkyllithiums, see: E. Kaufmann, J. Gose and P. v. R. Schleyer, Organometallics 8, 2577-2584 (1989); E. Kaufmann, K. Raghavachari, A. E. Reed and P. v. R. Schleyer, Organometallics 7, 1597-1607 (1988), and references cited therein. Here MeLi is just considered as a simple model for a generic alkyl group, and aggregation problems are plainly neglected. Not all alkyllithium have a strong inclination to aggregate: bulky t-BuLi. for instance, has been shown to exist as a monomer in tetrahydrofuran: W. Bauer, W. R. Winchester and P. v. R. Schleyer, Organometallics 6, 2371-2379 (1987). Theoretical studies carried out in this laboratory indicate that changing the structure of the anionic moiety by introduction of heteroatoms (Y) significantly affects the anion - cation interactions which determine the tendency to give aggregates; see, for Y=F, C. Canepa, P. Antoniotti and G. Tonachini, Tetrahedron 50, 8073-8084 (1994), and, for Y=Cl, C. Canepa and G. Tonachini, Tetrahedron 50, 12511-12520 (1994).
17. For the oligomerìzation of alkyllithiums, see: E. Kaufmann, J. Gose and P. v. R. Schleyer, Organometallics 8, 2577-2584 (1989); E. Kaufmann, K. Raghavachari, A. E. Reed and P. v. R. Schleyer, Organometallics 7, 1597-1607 (1988), and references cited therein. Here MeLi is just considered as a simple model for a generic alkyl group, and aggregation problems are plainly neglected. Not all alkyllithium have a strong inclination to aggregate: bulky t-BuLi. for instance, has been shown to exist as a monomer in tetrahydrofuran: W. Bauer, W. R. Winchester and P. v. R. Schleyer, Organometallics 6, 2371-2379 (1987). Theoretical studies carried out in this laboratory indicate that changing the structure of the anionic moiety by introduction of heteroatoms (Y) significantly affects the anion - cation interactions which determine the tendency to give aggregates; see, for Y=F, C. Canepa, P. Antoniotti and G. Tonachini, Tetrahedron 50, 8073-8084 (1994), and, for Y=Cl, C. Canepa and G. Tonachini, Tetrahedron 50, 12511-12520 (1994).
18. For the oligomerìzation of alkyllithiums, see: E. Kaufmann, J. Gose and P. v. R. Schleyer, Organometallics 8, 2577-2584 (1989); E. Kaufmann, K. Raghavachari, A. E. Reed and P. v. R. Schleyer, Organometallics 7, 1597-1607 (1988), and references cited therein. Here MeLi is just considered as a simple model for a generic alkyl group, and aggregation problems are plainly neglected. Not all alkyllithium have a strong inclination to aggregate: bulky t-BuLi. for instance, has been shown to exist as a monomer in tetrahydrofuran: W. Bauer, W. R. Winchester and P. v. R. Schleyer, Organometallics 6, 2371-2379 (1987). Theoretical studies carried out in this laboratory indicate that changing the structure of the anionic moiety by introduction of heteroatoms (Y) significantly affects the anion - cation interactions which determine the tendency to give aggregates; see, for Y=F, C. Canepa, P. Antoniotti and G. Tonachini, Tetrahedron 50, 8073-8084 (1994), and, for Y=Cl, C. Canepa and G. Tonachini, Tetrahedron 50, 12511-12520 (1994).
19. 2, OH, F) were also considered. A related study was carried out on the reaction of LiH with methane and acetylene (whose hydrogens exhibit a very different acidity); these reactions were found to proceed through four center transition structures, with very different activation barriers: E. Kaufmann, S. Sieber and P. v. R. Schleyer, J. Am. Chem. Soc. 111, 121-125 (1989).
20. 2, OH, F) were also considered. A related study was carried out on the reaction of LiH with methane and acetylene (whose hydrogens exhibit a very different acidity); these reactions were found to proceed through four center transition structures, with very different activation barriers: E. Kaufmann, S. Sieber and P. v. R. Schleyer, J. Am. Chem. Soc. 111, 121-125 (1989).
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28. (a) C. Møller and M. S. Plesset, Phys. Rev. 46, 618 (1934); J. S. Binkley and J. A. Pople, Int. J. Quantum Chem. 9, 229-236 (1975); J. A. Pople, J. S. Binkley and R. Seeger, Int. J. Quantum Chem. Symp. 10, -19 (1976); R. Krishnan and J. A. Pople, Int. J. Quantum Chem. 14, 91-100 (1978);
29. (a) C. Møller and M. S. Plesset, Phys. Rev. 46, 618 (1934); J. S. Binkley and J. A. Pople, Int. J. Quantum Chem. 9, 229-236 (1975); J. A. Pople, J. S. Binkley and R. Seeger, Int. J. Quantum Chem. Symp. 10, -19 (1976); R. Krishnan and J. A. Pople, Int. J. Quantum Chem. 14, 91-100 (1978);
30. (a) C. Møller and M. S. Plesset, Phys. Rev. 46, 618 (1934); J. S. Binkley and J. A. Pople, Int. J. Quantum Chem. 9, 229-236 (1975); J. A. Pople, J. S. Binkley and R. Seeger, Int. J. Quantum Chem. Symp. 10, -19 (1976); R. Krishnan and J. A. Pople, Int. J. Quantum Chem. 14, 91-100 (1978);
31. (b) J. A. Pople, R. Krishnan, H. B. Schlegel and J. S. Binkley, Int. J. Quantum. Chem. 14, 545-560 (1978); G. D. Purvis and R. J. Bartlett, J. Chem. Phys. 76, 1910-1918 (1982); G. E. Scuseria, C. L. Janssen and H. F. Schaefer, III, J. Chem. Phys. 89, 7382-7387 (1988); G. E. Scuseria and H. F. Schaefer, III, J. Chem. Phys. 90, 3700-3703 (1989); see also: R. J. Bartlett, Annu. Rev. Phys. Chem. 32, 359-401 ( 1981 ) for a discussion on these two methods and their performances.
32. (b) J. A. Pople, R. Krishnan, H. B. Schlegel and J. S. Binkley, Int. J. Quantum. Chem. 14, 545-560 (1978); G. D. Purvis and R. J. Bartlett, J. Chem. Phys. 76, 1910-1918 (1982); G. E. Scuseria, C. L. Janssen and H. F. Schaefer, III, J. Chem. Phys. 89, 7382-7387 (1988); G. E. Scuseria and H. F. Schaefer, III, J. Chem. Phys. 90, 3700-3703 (1989); see also: R. J. Bartlett, Annu. Rev. Phys. Chem. 32, 359-401 ( 1981 ) for a discussion on these two methods and their performances.
33. (b) J. A. Pople, R. Krishnan, H. B. Schlegel and J. S. Binkley, Int. J. Quantum. Chem. 14, 545-560 (1978); G. D. Purvis and R. J. Bartlett, J. Chem. Phys. 76, 1910-1918 (1982); G. E. Scuseria, C. L. Janssen and H. F. Schaefer, III, J. Chem. Phys. 89, 7382-7387 (1988); G. E. Scuseria and H. F. Schaefer, III, J. Chem. Phys. 90, 3700-3703 (1989); see also: R. J. Bartlett, Annu. Rev. Phys. Chem. 32, 359-401 ( 1981 ) for a discussion on these two methods and their performances.
34. (b) J. A. Pople, R. Krishnan, H. B. Schlegel and J. S. Binkley, Int. J. Quantum. Chem. 14, 545-560 (1978); G. D. Purvis and R. J. Bartlett, J. Chem. Phys. 76, 1910-1918 (1982); G. E. Scuseria, C. L. Janssen and H. F. Schaefer, III, J. Chem. Phys. 89, 7382-7387 (1988); G. E. Scuseria and H. F. Schaefer, III, J. Chem. Phys. 90, 3700-3703 (1989); see also: R. J. Bartlett, Annu. Rev. Phys. Chem. 32, 359-401 ( 1981 ) for a discussion on these two methods and their performances.
35. (b) J. A. Pople, R. Krishnan, H. B. Schlegel and J. S. Binkley, Int. J. Quantum. Chem. 14, 545-560 (1978); G. D. Purvis and R. J. Bartlett, J. Chem. Phys. 76, 1910-1918 (1982); G. E. Scuseria, C. L. Janssen and H. F. Schaefer, III, J. Chem. Phys. 89, 7382-7387 (1988); G. E. Scuseria and H. F. Schaefer, III, J. Chem. Phys. 90, 3700-3703 (1989); see also: R. J. Bartlett, Annu. Rev. Phys. Chem. 32, 359-401 ( 1981 ) for a discussion on these two methods and their performances.
36. (a) S. Huzinaga, J. Andzelm, M. Klobukowski, E. Radzio-Andzelm, Y. Sakai and H. Tatewaki, in Physical Sciences Data, Vol. 16. Elsevier, Amsterdam (1984);
37. (b) the basis consists, for K/C/Li/H, of (13s, 8p/7s, 5p, 1d/7s, 1p/4s) gaussians, respectively. These are grouped as 43321 (s) and 431 (p, the last one acting as a polarization set) for K, 421 (s), 311 (p, the last one a diffuse functions set) and 1 (d, a polarization set) for C, 421 (s) and 1 (p, a polarization set) for Li and 31 (s) for H. This grouping provides a [53/331/31/2] basis set, which is triple-ζ quality in the valence shell.
38. A. E. Reed, R. B. Weinstock and F. Weinhold, J. Chem. Phys. 83, 735-746(1985).
39. M. J. Frisch, G. W. Trucks, M. Head-Gordon, P. M. W. Gill, M. W. Wong, J. B. Foresman, B. G. Johnson, H. B. Schlegel, M. A. Robb, E. S. Replogle, R. Gomperts, J. L. Andres, K. Ragavachari, J. S. Binkley, C. Gonzales, R. I. Martin, D. J. Fox, D. J. Defrees, J. Baker, J. J. P. Stewart and J. A. Pople, Gaussian92. Gaussian, Pittsburgh, PA (1992).