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Volumn 65, Issue 7, 2000, Pages 2014-2021

Solvation and structural effects on the stability of 10-X-2 ate- complexes: A computational study

Author keywords

[No Author keywords available]

Indexed keywords

ALKYL GROUP; HALOGEN; LITHIUM; LITHIUM DERIVATIVE; ORGANOHALOGEN DERIVATIVE; POLYCYCLIC AROMATIC HYDROCARBON DERIVATIVE;

EID: 0034616318     PISSN: 00223263     EISSN: None     Source Type: Journal    
DOI: 10.1021/jo991511a     Document Type: Article
Times cited : (36)

References (58)
  • 4
  • 11
    • 0002772829 scopus 로고
    • For a review of the literature dealing with the mechanism of the lithium-halogen exchange reaction, see: Bailey, W. F.; Patricia, J. J. J. Organomet. Chem. 1988, 352, 1.
    • (1988) J. Organomet. Chem. , vol.352 , pp. 1
    • Bailey, W.F.1    Patricia, J.J.2
  • 12
    • 0001156760 scopus 로고
    • For a discussion of the mechanism of the exchange involving aliphatic substrates, see: (a) Bailey, W. F.; Gagnier, R. P.; Patricia, J. J. J. Org. Chem. 1984, 49, 2098. (b) Newcomb, M.; Williams, W. G.; Crumpacker, E. L. Tetrahedron Lett. 1985, 26, 1183 (c) Bailey, W. F.; Patricia, J. J.; Nurmi, T. T.; Wang, W. Tetrahedron Lett. 1986, 27, 1861. (d) Bailey, W. F.; Patricia, J. J.; Nurmi, T. T. Tetrahedron Lett. 1986, 27, 1865. (e) Ashby, E. C.; Pham, T. N. J. Org. Chem. 1987, 52, 1291. (f) Bailey, W. F.; Punzalan, E. R. J. Org. Chem. 1990, 55, 5404.
    • (1984) J. Org. Chem. , vol.49 , pp. 2098
    • Bailey, W.F.1    Gagnier, R.P.2    Patricia, J.J.3
  • 13
    • 0012103408 scopus 로고
    • For a discussion of the mechanism of the exchange involving aliphatic substrates, see: (a) Bailey, W. F.; Gagnier, R. P.; Patricia, J. J. J. Org. Chem. 1984, 49, 2098. (b) Newcomb, M.; Williams, W. G.; Crumpacker, E. L. Tetrahedron Lett. 1985, 26, 1183 (c) Bailey, W. F.; Patricia, J. J.; Nurmi, T. T.; Wang, W. Tetrahedron Lett. 1986, 27, 1861. (d) Bailey, W. F.; Patricia, J. J.; Nurmi, T. T. Tetrahedron Lett. 1986, 27, 1865. (e) Ashby, E. C.; Pham, T. N. J. Org. Chem. 1987, 52, 1291. (f) Bailey, W. F.; Punzalan, E. R. J. Org. Chem. 1990, 55, 5404.
    • (1985) Tetrahedron Lett. , vol.26 , pp. 1183
    • Newcomb, M.1    Williams, W.G.2    Crumpacker, E.L.3
  • 14
    • 0000754130 scopus 로고
    • For a discussion of the mechanism of the exchange involving aliphatic substrates, see: (a) Bailey, W. F.; Gagnier, R. P.; Patricia, J. J. J. Org. Chem. 1984, 49, 2098. (b) Newcomb, M.; Williams, W. G.; Crumpacker, E. L. Tetrahedron Lett. 1985, 26, 1183 (c) Bailey, W. F.; Patricia, J. J.; Nurmi, T. T.; Wang, W. Tetrahedron Lett. 1986, 27, 1861. (d) Bailey, W. F.; Patricia, J. J.; Nurmi, T. T. Tetrahedron Lett. 1986, 27, 1865. (e) Ashby, E. C.; Pham, T. N. J. Org. Chem. 1987, 52, 1291. (f) Bailey, W. F.; Punzalan, E. R. J. Org. Chem. 1990, 55, 5404.
    • (1986) Tetrahedron Lett. , vol.27 , pp. 1861
    • Bailey, W.F.1    Patricia, J.J.2    Nurmi, T.T.3    Wang, W.4
  • 15
    • 0000844315 scopus 로고
    • For a discussion of the mechanism of the exchange involving aliphatic substrates, see: (a) Bailey, W. F.; Gagnier, R. P.; Patricia, J. J. J. Org. Chem. 1984, 49, 2098. (b) Newcomb, M.; Williams, W. G.; Crumpacker, E. L. Tetrahedron Lett. 1985, 26, 1183 (c) Bailey, W. F.; Patricia, J. J.; Nurmi, T. T.; Wang, W. Tetrahedron Lett. 1986, 27, 1861. (d) Bailey, W. F.; Patricia, J. J.; Nurmi, T. T. Tetrahedron Lett. 1986, 27, 1865. (e) Ashby, E. C.; Pham, T. N. J. Org. Chem. 1987, 52, 1291. (f) Bailey, W. F.; Punzalan, E. R. J. Org. Chem. 1990, 55, 5404.
    • (1986) Tetrahedron Lett. , vol.27 , pp. 1865
    • Bailey, W.F.1    Patricia, J.J.2    Nurmi, T.T.3
  • 16
    • 0000690753 scopus 로고
    • For a discussion of the mechanism of the exchange involving aliphatic substrates, see: (a) Bailey, W. F.; Gagnier, R. P.; Patricia, J. J. J. Org. Chem. 1984, 49, 2098. (b) Newcomb, M.; Williams, W. G.; Crumpacker, E. L. Tetrahedron Lett. 1985, 26, 1183 (c) Bailey, W. F.; Patricia, J. J.; Nurmi, T. T.; Wang, W. Tetrahedron Lett. 1986, 27, 1861. (d) Bailey, W. F.; Patricia, J. J.; Nurmi, T. T. Tetrahedron Lett. 1986, 27, 1865. (e) Ashby, E. C.; Pham, T. N. J. Org. Chem. 1987, 52, 1291. (f) Bailey, W. F.; Punzalan, E. R. J. Org. Chem. 1990, 55, 5404.
    • (1987) J. Org. Chem. , vol.52 , pp. 1291
    • Ashby, E.C.1    Pham, T.N.2
  • 17
    • 0001043464 scopus 로고
    • For a discussion of the mechanism of the exchange involving aliphatic substrates, see: (a) Bailey, W. F.; Gagnier, R. P.; Patricia, J. J. J. Org. Chem. 1984, 49, 2098. (b) Newcomb, M.; Williams, W. G.; Crumpacker, E. L. Tetrahedron Lett. 1985, 26, 1183 (c) Bailey, W. F.; Patricia, J. J.; Nurmi, T. T.; Wang, W. Tetrahedron Lett. 1986, 27, 1861. (d) Bailey, W. F.; Patricia, J. J.; Nurmi, T. T. Tetrahedron Lett. 1986, 27, 1865. (e) Ashby, E. C.; Pham, T. N. J. Org. Chem. 1987, 52, 1291. (f) Bailey, W. F.; Punzalan, E. R. J. Org. Chem. 1990, 55, 5404.
    • (1990) J. Org. Chem. , vol.55 , pp. 5404
    • Bailey, W.F.1    Punzalan, E.R.2
  • 18
    • 0001763436 scopus 로고
    • For a discussion of the mechanism of Organolithium-aryl halide exchange, see: (a) Winkler, H. J. S.; Winkler, H. J. Am. Chem. Soc. 1966, 88, 964. (b) Winkler, H. J. S.; Winkler, H. J. Am. Chem. Soc. 1966, 88, 969. (c) Rogers, H. R.; Houk, J. J. Am. Chem. Soc. 1982, 104, 522. (d) Beak, P.; Allen, D. J.; Lee, W. K. J. Am. Chem. Soc. 1990, 112, 1629. (e) Beak, P.; Allen, D. J. J. Am. Chem. Soc. 1992, 114, 3420.
    • (1966) J. Am. Chem. Soc. , vol.88 , pp. 964
    • Winkler, H.J.S.1    Winkler, H.2
  • 19
    • 0001645228 scopus 로고
    • For a discussion of the mechanism of Organolithium-aryl halide exchange, see: (a) Winkler, H. J. S.; Winkler, H. J. Am. Chem. Soc. 1966, 88, 964. (b) Winkler, H. J. S.; Winkler, H. J. Am. Chem. Soc. 1966, 88, 969. (c) Rogers, H. R.; Houk, J. J. Am. Chem. Soc. 1982, 104, 522. (d) Beak, P.; Allen, D. J.; Lee, W. K. J. Am. Chem. Soc. 1990, 112, 1629. (e) Beak, P.; Allen, D. J. J. Am. Chem. Soc. 1992, 114, 3420.
    • (1966) J. Am. Chem. Soc. , vol.88 , pp. 969
    • Winkler, H.J.S.1    Winkler, H.2
  • 20
    • 0001763419 scopus 로고
    • For a discussion of the mechanism of Organolithium-aryl halide exchange, see: (a) Winkler, H. J. S.; Winkler, H. J. Am. Chem. Soc. 1966, 88, 964. (b) Winkler, H. J. S.; Winkler, H. J. Am. Chem. Soc. 1966, 88, 969. (c) Rogers, H. R.; Houk, J. J. Am. Chem. Soc. 1982, 104, 522. (d) Beak, P.; Allen, D. J.; Lee, W. K. J. Am. Chem. Soc. 1990, 112, 1629. (e) Beak, P.; Allen, D. J. J. Am. Chem. Soc. 1992, 114, 3420.
    • (1982) J. Am. Chem. Soc. , vol.104 , pp. 522
    • Rogers, H.R.1    Houk, J.2
  • 21
    • 0001066613 scopus 로고
    • For a discussion of the mechanism of Organolithium-aryl halide exchange, see: (a) Winkler, H. J. S.; Winkler, H. J. Am. Chem. Soc. 1966, 88, 964. (b) Winkler, H. J. S.; Winkler, H. J. Am. Chem. Soc. 1966, 88, 969. (c) Rogers, H. R.; Houk, J. J. Am. Chem. Soc. 1982, 104, 522. (d) Beak, P.; Allen, D. J.; Lee, W. K. J. Am. Chem. Soc. 1990, 112, 1629. (e) Beak, P.; Allen, D. J. J. Am. Chem. Soc. 1992, 114, 3420.
    • (1990) J. Am. Chem. Soc. , vol.112 , pp. 1629
    • Beak, P.1    Allen, D.J.2    Lee, W.K.3
  • 22
    • 85022693248 scopus 로고
    • For a discussion of the mechanism of Organolithium-aryl halide exchange, see: (a) Winkler, H. J. S.; Winkler, H. J. Am. Chem. Soc. 1966, 88, 964. (b) Winkler, H. J. S.; Winkler, H. J. Am. Chem. Soc. 1966, 88, 969. (c) Rogers, H. R.; Houk, J. J. Am. Chem. Soc. 1982, 104, 522. (d) Beak, P.; Allen, D. J.; Lee, W. K. J. Am. Chem. Soc. 1990, 112, 1629. (e) Beak, P.; Allen, D. J. J. Am. Chem. Soc. 1992, 114, 3420.
    • (1992) J. Am. Chem. Soc. , vol.114 , pp. 3420
    • Beak, P.1    Allen, D.J.2
  • 25
    • 0012072664 scopus 로고
    • and references therein
    • (c) Ward, H. R. Acc. Chem. Res. 1972, 5, 18 and references therein.
    • (1972) Acc. Chem. Res. , vol.5 , pp. 18
    • Ward, H.R.1
  • 29
    • 0343657573 scopus 로고
    • Gilman's group appears to have been the first to suggest that lithium-halogen exchange may proceed via nucleophilic attack of an organolithium on the halogen atom of an organic halide. This early mechanistic formulation viewed the exchange as an SN2-like process in which a hypervalent 10-X-2 species would be the transition state, see: Sunthankar, S. V.; Gilman, H. J. Org. Chem. 1951, 16, 123.
    • (1951) J. Org. Chem. , vol.16 , pp. 123
    • Sunthankar, S.V.1    Gilman, H.2
  • 30
    • 0002871621 scopus 로고
    • Wittig and Schöllkopf appear to have been the first to suggest that nucleophilic attack by an organolithium on the halogen atom of a substrate may give a 10-X-2 species as an intermediate, see: Wittig, G.; Schöllkopf, U. Tetrahedron Lett. 1958, 3, 91. The putative 10-X-2 intermediate was termed an "ate-complex" by Wittig, see: Wittig, G. Angew. Chem. 1958, 70, 65.
    • (1958) Tetrahedron Lett. , vol.3 , pp. 91
    • Wittig, G.1    Schöllkopf, U.2
  • 31
    • 0002871621 scopus 로고
    • Wittig and Schöllkopf appear to have been the first to suggest that nucleophilic attack by an organolithium on the halogen atom of a substrate may give a 10-X-2 species as an intermediate, see: Wittig, G.; Schöllkopf, U. Tetrahedron Lett. 1958, 3, 91. The putative 10-X-2 intermediate was termed an "ate-complex" by Wittig, see: Wittig, G. Angew. Chem. 1958, 70, 65.
    • (1958) Angew. Chem. , vol.70 , pp. 65
    • Wittig, G.1
  • 42
    • 0342787336 scopus 로고    scopus 로고
    • note
    • +. This species, which was prepared by Farnham and Calabrese (ref 15), was fully characterized but structural data were not reported.
  • 47
    • 0000073015 scopus 로고    scopus 로고
    • A recent theoretical investigation of the role of solvation on a model lithium-iodine exchange reaction between methyl iodide and vinyllithium indicates that introduction of a single water molecule as a ligand for lithium lowers the activation energy, leading to a 10-I-2 complex transition state for the process, see: Jedlicka, B.; Crabtree, R. H.; Siegbahn, P. E. M. Organometallics 1997, 16, 6021.
    • (1997) Organometallics , vol.16 , pp. 6021
    • Jedlicka, B.1    Crabtree, R.H.2    Siegbahn, P.E.M.3
  • 55
    • 0343221891 scopus 로고    scopus 로고
    • note
    • Detailed structural data may be found in the Supporting Information.
  • 56
    • 0343657567 scopus 로고    scopus 로고
    • note
    • 2v symmetry are reported by Boche, Cioslowski, and co-workers (ref 19b) to be 22.6, 28.2, and 33.4 kcal/mol for X = I, Br, and Cl, respectively.
  • 57
    • 0343221889 scopus 로고    scopus 로고
    • note
    • 3F. The calculated bond lengths for the lithium halides are 2.435 Å for LiI, 2.195 Å for LiBr, 2.055 Å for LiCl, and 1.584 Å for LiF.


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