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Volumn 117, Issue 11, 1995, Pages 3205-3222

Reactivity Paradigms: Transition State Structure, Mechanisms of Barrier Formation, and Stereospecificity of Nucleophilic Substitutions on σ-Cation Radicals

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EID: 0001206104     PISSN: 00027863     EISSN: 15205126     Source Type: Journal    
DOI: 10.1021/ja00116a025     Document Type: Article
Times cited : (31)

References (85)
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    • 2 terminus which also has the highest HOMO coefficient in the ground state ketene and the highest SOMO coefficient in the cation radical ketene. We note that the site with the highest LUMO coefficient is disfavored due to instability of the respective addition product
    • 2 terminus which also has the highest HOMO coefficient in the ground state ketene and the highest SOMO coefficient in the cation radical ketene. We note that the site with the highest LUMO coefficient is disfavored due to instability of the respective addition product.
    • Shaik, S.1    Ioffe, A.2
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    • For the analysis of regioselectivity in radical addition to olefins and for the identity of the site with the highest triplet spin density to the site with the highest HOMO density, see
    • (b) For the analysis of regioselectivity in radical addition to olefins and for the identity of the site with the highest triplet spin density to the site with the highest HOMO density, see: Shaik, S. S.; Canadell, E. J. Am. Chem. Soc. 1990, 112, 1446.
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    • For an alternative VB analysis of MO based wavefunctions
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    • le is the one-electron bond energy of the cation radical, and MCA is the methyl cation affinity or in the general case the alkyl (silyl) cation affinity. MCA values are taken from the Meot-Ner, M.
    • le is the one-electron bond energy of the cation radical, and MCA is the methyl cation affinity or in the general case the alkyl (silyl) cation affinity. MCA values are taken from the Meot-Ner, M.; Karpas, Z.; Deakyne, C. A. J. Am. Chem. Soc. 1986, 108, 3913.
    • (1986) J. Am. Chem. Soc. , vol.108 , pp. 3913
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    • •+ and a general discussion of its reactivity, inter alia, see
    • •+ and a general discussion of its reactivity, inter alia, see: Stirk, K. M.; Kiminkinen, L. K. M.; Kenttamaa, H. I. Chem. Rev. 1992, 92, 1649.
    • (1992) Chem. Rev. , vol.92 , pp. 1649
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    • For a related discussion see ref 24a
    • (c) For a related discussion see ref 24a.
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    • (1989) New Theoretical Concepts for Understanding Organic Reactions , vol.C267 , pp. 165-218
    • Shaik, S.S.1
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    • 2 in eq 8 is not unity because ΦSub and Φetshare a common determinant. For normalization constants of VB wave functions see the Appendix of ref 42 and the Appendix in the following
    • 2 in eq 8 is not unity because ΦSub and Φetshare a common determinant. For normalization constants of VB wave functions see the Appendix of ref 42 and the Appendix in the following: Shaik, S. S.; Duzy, E.; Bartuv, A. J. Phys. Chem. 1990, 94, 6574.
    • (1990) J. Phys. Chem. , vol.94 , pp. 6574
    • Shaik, S.S.1    Duzy, E.2    Bartuv, A.3
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    • • is 75% triplet. For discussion of such a three-electron wave function, see (especially Appendix 1).
    • • is 75% triplet. For discussion of such a three-electron wave function, see: Shaik, S.; Hiberty, P. C.; Lefour, J. M.; Ohanessian, G. J. Am. Chem. Soc. 1987, 109, 363 (especially Appendix 1).
    • (1987) J. Am. Chem. Soc. , vol.109 , pp. 363
    • Shaik, S.1    Hiberty, P.C.2    Lefour, J.M.3    Ohanessian, G.4
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    • For the definition of the PRS of a chemical reaction, see Shaik, S. Faraday Trans. 1994, 90, 1671 PRS replaces the term ACS used previously (ref 21).
    • For the definition of the PRS of a chemical reaction, see: Truhlar, D. G. Faraday Trans. 1994, 90, 1670. Shaik, S. Faraday Trans. 1994, 90, 1671. PRS replaces the term ACS used previously (ref 21).
    • (1994) Faraday Trans. , vol.90 , pp. 1670
    • Truhlar, D.G.1
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    • For the use of these three configurations to describe the curve crossing situation of cation radical decomposition, see
    • For the use of these three configurations to describe the curve crossing situation of cation radical decomposition, see: Takahashi, O.; Kikuchi, O. Tetrahedron Lett. 1991, 37, 4933.
    • (1991) Tetrahedron Lett , vol.37 , pp. 4933
    • Takahashi, O.1    Kikuchi, O.2
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