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Volumn , Issue 3, 1997, Pages 463-472

Radical cations of non-alternant systems as probes of the Shaik-Pross VB configuration mixing model

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EID: 0343107934     PISSN: 03009580     EISSN: None     Source Type: Journal    
DOI: 10.1039/a606702f     Document Type: Article
Times cited : (23)

References (96)
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  • 2
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    • For reviews on radical cation reactivity, see: O. Hammerich and V. D. Parker, Adv. Phys. Org. Chem., 1984, 20, 55; A. J. Bard, A. Ledwith and H. J. Shine, Adv. Phys. Org. Chem., 1976, 12, 155.
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    • See, e.g.: (a) V. D. Parker, B. Reitstöen and M. Tilset, J. Phys. Org. Chem., 1989, 2, 580; (b) B. Reitstöen, F. Norrsell and V. D. Parker, J. Am. Chem. Soc., 1989, 111, 8463; (c) T. Drewello, N. Heinrich, N. W. M. P. Mass, N. M. M. Nibbering, T. Weiske and H. Schwarz, J. Am. Chem. Soc., 1987, 109, 4810; (d) J. P. Dinnocenzo, S. Farid, S. J. L. Goodman, I. R. Gould and W. P. Todd, Mol. Crysy. Liq. Cryst., 1991, 194, 151.
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    • See, e.g.: (a) V. D. Parker, B. Reitstöen and M. Tilset, J. Phys. Org. Chem., 1989, 2, 580; (b) B. Reitstöen, F. Norrsell and V. D. Parker, J. Am. Chem. Soc., 1989, 111, 8463; (c) T. Drewello, N. Heinrich, N. W. M. P. Mass, N. M. M. Nibbering, T. Weiske and H. Schwarz, J. Am. Chem. Soc., 1987, 109, 4810; (d) J. P. Dinnocenzo, S. Farid, S. J. L. Goodman, I. R. Gould and W. P. Todd, Mol. Crysy. Liq. Cryst., 1991, 194, 151.
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    • See, e.g.: (a) V. D. Parker, B. Reitstöen and M. Tilset, J. Phys. Org. Chem., 1989, 2, 580; (b) B. Reitstöen, F. Norrsell and V. D. Parker, J. Am. Chem. Soc., 1989, 111, 8463; (c) T. Drewello, N. Heinrich, N. W. M. P. Mass, N. M. M. Nibbering, T. Weiske and H. Schwarz, J. Am. Chem. Soc., 1987, 109, 4810; (d) J. P. Dinnocenzo, S. Farid, S. J. L. Goodman, I. R. Gould and W. P. Todd, Mol. Crysy. Liq. Cryst., 1991, 194, 151.
    • (1987) J. Am. Chem. Soc. , vol.109 , pp. 4810
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    • See, e.g.: (a) V. D. Parker, B. Reitstöen and M. Tilset, J. Phys. Org. Chem., 1989, 2, 580; (b) B. Reitstöen, F. Norrsell and V. D. Parker, J. Am. Chem. Soc., 1989, 111, 8463; (c) T. Drewello, N. Heinrich, N. W. M. P. Mass, N. M. M. Nibbering, T. Weiske and H. Schwarz, J. Am. Chem. Soc., 1987, 109, 4810; (d) J. P. Dinnocenzo, S. Farid, S. J. L. Goodman, I. R. Gould and W. P. Todd, Mol. Crysy. Liq. Cryst., 1991, 194, 151.
    • (1991) Mol. Crysy. Liq. Cryst. , vol.194 , pp. 151
    • Dinnocenzo, J.P.1    Farid, S.2    Goodman, S.J.L.3    Gould, I.R.4    Todd, W.P.5
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    • note
    • -1. For a revised B value, see ref. 6(c).
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    • Springer, Heidelberg
    • For anodic substitution reactions, see K. Yoshida, Electroxidation in Organic Chemistry. The Role of Cation Radicals as Synthetic Intermediates, Wiley, New York, 1984. For metal ion promoted acetoxylation, see L. Eberson, Electron Transfer Reactions in Organic Chemistry, Springer, Heidelberg, 1987, pp. 80-82.
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    • note
    • As explained in ref. 6(c) this curve crossing does not occur for cases where the nucleophile is neutral and has a high ionization potential. Even so, the VB mixing will involve the same configuration types.
  • 29
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    • note
    • (c) note in (a) that only when the stability differs markedly does the regioselectivity follow strictly the relative stability of the isomers.
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    • New Theoretical Concepts for Understanding Organic Reactions
    • eds. J. Bertran and I. G. Csizmadia, Kluwer, Netherlands
    • The orbitals of these configurations correspond to the situation at the crossing point. These are effective configurations which include the effect of other configurations through the adaptation of the orbitals to the requisite mixing at the transition state. For discussions, see: (a) S. Shaik, in New Theoretical Concepts for Understanding Organic Reactions, eds. J. Bertran and I. G. Csizmadia, NATO ASI Series, Vol. C. 267, Kluwer, Netherlands, 1989, pp. 165-217; (b) S. Shaik and P. C. Hiberty, Adv. Quant. Chem., 1995, 26, 99.
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    • The orbitals of these configurations correspond to the situation at the crossing point. These are effective configurations which include the effect of other configurations through the adaptation of the orbitals to the requisite mixing at the transition state. For discussions, see: (a) S. Shaik, in New Theoretical Concepts for Understanding Organic Reactions, eds. J. Bertran and I. G. Csizmadia, NATO ASI Series, Vol. C. 267, Kluwer, Netherlands, 1989, pp. 165-217; (b) S. Shaik and P. C. Hiberty, Adv. Quant. Chem., 1995, 26, 99.
    • (1995) Adv. Quant. Chem. , vol.26 , pp. 99
    • Shaik, S.1    Hiberty, P.C.2
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    • ed. J. P. Snyder, Academic Press, New York, ch. 1 and references cited therein
    • R. Zahradnik, in Non-benzenoid Aromatics, ed. J. P. Snyder, vol. II, Academic Press, New York, 1971, ch. 1 and references cited therein.
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    • For reviews, see: (a) L. Eberson, M. P. Hartshorn and F. Radner, Acta Chem. Scand., 1994, 48, 937; (b) L. Eberson, M. P. Hartshorn and F. Radner, in Advances in Carbocation Chemistry, vol. 2, JAI Press, 1995, 207-263.
    • (1994) Acta Chem. Scand. , vol.48 , pp. 937
    • Eberson, L.1    Hartshorn, M.P.2    Radner, F.3
  • 57
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    • The complete active space self-consistent field method and its application in electronic structure calculations
    • ed., K. P. Lawley, Wiley, Chichester, England, ch. 69
    • B. O. Roos, The complete active space self-consistent field method and its application in electronic structure calculations, in ed., K. P. Lawley, Advances in Chemical Physics; Ab Initio Methods in Quantum Chemislry-II, Wiley, Chichester, England, 1987, ch. 69, p. 399.
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    • note
    • 2, respectively. The molecules are placed in the yz plane. Therefore the second and fourth symmetries correspond to π-orbitals.


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