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Volumn 104, Issue 26, 1982, Pages 7599-7609

Transition-State Barrier for Electrophilic Reactions. Solvation of Charge-Transfer Ion Pairs as the Unifying Factor in Alkene Addition and Aromatic Substitution with Bromine

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EID: 0001504721     PISSN: 00027863     EISSN: 15205126     Source Type: Journal    
DOI: 10.1021/ja00390a035     Document Type: Article
Times cited : (82)

References (120)
  • 4
    • 84918140116 scopus 로고
    • Zabieky, J., Ed.; Wiley-Interscience: New York
    • Schmid, G. H.; Garratt, D. G. In “Chemistry of Alkenes”; Zabieky, J., Ed.; Wiley-Interscience: New York, 1977; Vol. 3.
    • (1977) Chemistry of Alkenes , vol.3
    • Schmid, G.H.1    Garratt, D.G.2
  • 25
    • 36849118220 scopus 로고
    • For theoretical approaches to electrophilic reactions, see
    • For theoretical approaches to electrophilic reactions, see: Fukui, K.; Yonezawa, T.; Nagata, C.; Shingu, H. J. Chem. Phys. 1954, 22, 1433.
    • (1954) J. Chem. Phys. , vol.22 , pp. 1433
    • Fukui, K.1    Yonezawa, T.2    Nagata, C.3    Shingu, H.4
  • 34
    • 0010591540 scopus 로고
    • For the basis of the CT formulation for organometallic and other donors, see
    • For the basis of the CT formulation for organometallic and other donors, see: Fukuzumi, S.; Kochi, J. K. J. Phys. Chem. 1980, 84, 2246, 2254.
    • (1980) J. Phys. Chem. , vol.84
    • Fukuzumi, S.1    Kochi, J.K.2
  • 35
    • 0000362410 scopus 로고
    • and references therein
    • Kochi, J. K. Pure Appt. Chem. 1980, 52, 571 and references therein.
    • (1980) Pure Appt. Chem. , vol.52 , pp. 571
    • Kochi, J.K.1
  • 44
    • 84985369971 scopus 로고
    • −1; ΔS = −16 eu) are characteristic of weak intermolecular complexes
    • −1; ΔS = −16 eu) are characteristic of weak intermolecular complexes.
    • (1967) Teor. Eksp. Khim. , vol.3 , pp. 240
    • Sergeev, G.B.1    Chen, T.2
  • 45
    • 0142130121 scopus 로고
    • See:, Foster, R., Ed.; Academic Press: New York, Chapter 5
    • See: Tamres, M.; Strong, R. L. “Molecular Association”; Foster, R., Ed.; Academic Press: New York, 1979; Vol. 2, Chapter 5.
    • (1979) Molecular Association , vol.2
    • Tamres, M.1    Strong, R.L.2
  • 47
    • 85021570972 scopus 로고    scopus 로고
    • For a discussion of the second- and third-order rate constants as they apply to the CT mechanism, see:, in press
    • For a discussion of the second- and third-order rate constants as they apply to the CT mechanism, see: Fukuzumi, S.; Kochi, J. K. Int. J. Chem. Kinet., in press.
    • Int. J. Chem. Kinet.
    • Fukuzumi, S.1    Kochi, J.K.2
  • 50
    • 0003396198 scopus 로고
    • Br-(MeOH) − 2.23 from ref 21 with the data from
    • Br-(MeOH) − 2.23 from ref 21 with the data from: Dubois, J. E.; Mouvier, G. Tetrahedron Lett. 1963, 1325.
    • (1963) Tetrahedron Lett. , pp. 1325
    • Dubois, J.E.1    Mouvier, G.2
  • 56
    • 0004029492 scopus 로고
    • The nature of the CT excited state of the π-type EDA complexes has been experimentally verified to be the polar ion pair by applying spectroscopic methods with pulsed laser excitation in accord with the Mulliken theory. See:, Foster, R., Ed.; Academic Press: New York, and references cited therein
    • The nature of the CT excited state of the π-type EDA complexes has been experimentally verified to be the polar ion pair by applying spectroscopic methods with pulsed laser excitation in accord with the Mulliken theory. See: Mataga, N.; Ottolenghi, M. In “Molecular Association”; Foster, R., Ed.; Academic Press: New York, 1979; Vol. 2, p 31 and references cited therein.
    • (1979) Molecular Association , vol.2 , pp. 31
    • Mataga, N.1    Ottolenghi, M.2
  • 57
    • 0141895388 scopus 로고
    • Lim, E. C., Ed.; Academic Press: New York
    • Nagakura, S. “Excited States”; Lim, E. C., Ed.; Academic Press: New York, 1975; Vol. 2, p 334.
    • (1975) Excited States , vol.2 , pp. 334
    • Nagakura, S.1
  • 61
    • 33847089778 scopus 로고
    • k(DA*) in eq a and b is unlikely for weak complexes. For the nature of in molecular complexes, see
    • k(DA*) in eq a and b is unlikely for weak complexes. For the nature of in molecular complexes, see: Morokuma, K. Acc. Chem. Res. 1977, 10, 294.]
    • (1977) Acc. Chem. Res. , vol.10 , pp. 294
    • Morokuma, K.1
  • 62
    • 2742611721 scopus 로고
    • Dwith a unit slope (compare Figure 2), provided the interaction energy ω remains invariant in a series of EDA complexes involving a family of structurally related donors. Such a correlation is tantamount to a constant steric effect, since ω reflects the mean separation between the donor and acceptor moieties in the EDA complex. [For a discussion of steric effects in arene complexes, see
    • Dwith a unit slope (compare Figure 2), provided the interaction energy ω remains invariant in a series of EDA complexes involving a family of structurally related donors. Such a correlation is tantamount to a constant steric effect, since ω reflects the mean separation between the donor and acceptor moieties in the EDA complex. [For a discussion of steric effects in arene complexes, see: Fukuzumi, S.; Kochi, J. K. Phys. Chem. 1981, 85, 648;
    • (1981) Phys. Chem. , vol.85 , pp. 648
    • Fukuzumi, S.1    Kochi, J.K.2
  • 63
    • 85088543834 scopus 로고
    • and for steric effects in halogen complexes, see:, Thus for weak complexes, Mulliken theory predicts an excited ion-pair state in which the mean separation is the same as that in the EDA complex itself. For the experimental verification of CT ion pairs, see ref 26
    • and for steric effects in halogen complexes, see: Fukuzumi, S.; Kochi, J. K. Phys. Chem. 1980, 84, 608, 617.] Thus for weak complexes, Mulliken theory predicts an excited ion-pair state in which the mean separation is the same as that in the EDA complex itself. For the experimental verification of CT ion pairs, see ref 26.
    • (1980) Phys. Chem. , vol.84
    • Fukuzumi, S.1    Kochi, J.K.2
  • 66
    • 0039893277 scopus 로고
    • Foster, R., Ed.; Academic Press: New York, Chapter 3
    • Davis, K. M. C. In “Molecular Association”; Foster, R., Ed.; Academic Press: New York, 1975; Vol. 1, Chapter 3.
    • (1975) Molecular Association , vol.1
    • Davis, K.M.C.1
  • 67
    • 21944431525 scopus 로고
    • −1for the tetracyanobenzenetoluene EDA complex in toluene. These experiments were verified (using a pulsed nitrogen laser excitation) as a time-dependent (1–100 ns) red shift of the fluorescence of the excited TCNB-toluene EDA complex, which directly reflects the solvent reorientation
    • −1for the tetracyanobenzenetoluene EDA complex in toluene. These experiments were verified (using a pulsed nitrogen laser excitation) as a time-dependent (1–100 ns) red shift of the fluorescence of the excited TCNB-toluene EDA complex, which directly reflects the solvent reorientation. (Egawa, K.; Nakashima, N.; Mataga, N.; Yamanaka, C. Chem. Phys. Lett. 1971, 8, 108;
    • (1971) Chem. Phys. Lett. , vol.8 , pp. 108
    • Egawa, K.1    Nakashima, N.2    Mataga, N.3    Yamanaka, C.4
  • 68
    • 0010390567 scopus 로고
    • 29When the solvation of the TCNB anion and the difference of the solvent are taken into account, the solvation in the equilibrium fluorescent state may be approximated by the sum of the solvation of each cation and anion. Thus, the Stokes shift in the fluorescence of the excited EDA complexes could provide further insight into the solvent effects in the electrophilic aromatic substitutions on the absolute scale
    • 29When the solvation of the TCNB anion and the difference of the solvent are taken into account, the solvation in the equilibrium fluorescent state may be approximated by the sum of the solvation of each cation and anion. Thus, the Stokes shift in the fluorescence of the excited EDA complexes could provide further insight into the solvent effects in the electrophilic aromatic substitutions on the absolute scale.
    • (1971) Bull. Chem. Soc. Jpn. , vol.44 , pp. 3287
  • 69
    • 0003920239 scopus 로고
    • For the treatment of solvation in adiabatic electron-transfer processes, see:, Ronald Press: New York
    • For the treatment of solvation in adiabatic electron-transfer processes, see: Reynolds, W. L.; Lumry, R. W. “Mechanisms of Electron Transfer”; Ronald Press: New York, 1966.
    • (1966) Mechanisms of Electron Transfer
    • Reynolds, W.L.1    Lumry, R.W.2
  • 71
    • 0001301822 scopus 로고
    • For inorganic systems, see
    • For inorganic systems, see: Dulz, G.; Sutin, N. Inorg. Chem. 1963, 2, 917.
    • (1963) Inorg. Chem. , vol.2 , pp. 917
    • Dulz, G.1    Sutin, N.2
  • 78
    • 0001438690 scopus 로고
    • Can. J. Chem. 1977, 55, 2900.
    • (1977) Can. J. Chem. , vol.55 , pp. 2900
  • 80
    • 33847087736 scopus 로고
    • For the importance of outer-sphere mechanisms in electron transfer, see
    • For the importance of outer-sphere mechanisms in electron transfer, see: Wong, C. L.; Fukuzumi, S.; Kochi, J. K. J. Am. Chem. Soc. 1980, 102, 2928.
    • (1980) J. Am. Chem. Soc. , vol.102 , pp. 2928
    • Wong, C.L.1    Fukuzumi, S.2    Kochi, J.K.3
  • 82
    • 85021532894 scopus 로고
    • 3+later. For the products derived from the oxidation of alkenes by various 1-equiv oxidants, see the review by:, Patai, S., Ed.; Wiley: New York, Chapter 11
    • 3+later. For the products derived from the oxidation of alkenes by various 1-equiv oxidants, see the review by: Henry, P. M.; Lange, G. L. In “Chemistry of Double-Bonded Functional Groups”; Patai, S., Ed.; Wiley: New York, 1977; Suppl. A., Part 2, Chapter 11.
    • (1977) Chemistry of Double-Bonded Functional Groups , Issue.Part 2
    • Henry, P.M.1    Lange, G.L.2
  • 89
    • 85021537674 scopus 로고
    • For typical products of 1-equiv oxidation of aromatic compounds, see the reviews by
    • For typical products of 1-equiv oxidation of aromatic compounds, see the reviews by: Littler, J. S.; Nonhebel, D. C. Int. Rev. Sci., Org. Chem. Ser. Two 1975, 10, 212.
    • (1975) Int. Rev. Sci., Org. Chem. Ser. Two , vol.10 , pp. 212
    • Littler, J.S.1    Nonhebel, D.C.2
  • 93
    • 84985415729 scopus 로고
    • This follows from the general form of the free energy relationship applicable to the endergonic region, see:, See also ref 34
    • This follows from the general form of the free energy relationship applicable to the endergonic region, see: Agmon, N. Int. J. Chem. Kinet. 1981, 13, 333. See also ref 34.
    • (1981) Int. J. Chem. Kinet. , vol.13 , pp. 333
    • Agmon, N.1
  • 94
    • 0012566066 scopus 로고
    • The solvation of the neutral species is neglected in comparison with that of the donor cation
    • The solvation of the neutral species is neglected in comparison with that of the donor cation (Lofti, M.; Roberts, R. M. G. Tetrahedron 1979, 35, 2137.
    • (1979) Tetrahedron , vol.35 , pp. 2137
    • Lofti, M.1    Roberts, R.M.G.2
  • 96
    • 0001589004 scopus 로고
    • It is also assumed that the vertical and adiabatic cations have essentially the same structure. However, see
    • It is also assumed that the vertical and adiabatic cations have essentially the same structure. However, see: Bellville, D. J.; Bauld, N. L. J. Am. Chem. Soc. 1982, 104, 294.
    • (1982) J. Am. Chem. Soc. , vol.104 , pp. 294
    • Bellville, D.J.1    Bauld, N.L.2
  • 97
    • 85021562602 scopus 로고
    • ox+ constant can be measured electrochemically. (See ref 14 and:, Hush, N. S., Ed.; Wiley: New York
    • ox+ constant can be measured electrochemically. (See ref 14 and: Case, B. In “Reactions of Molecules at Electrodes”; Hush, N. S., Ed.; Wiley: New York, 1971; p 125.
    • (1971) Reactions of Molecules at Electrodes , pp. 125
    • Case, B.1
  • 105
    • 0038619561 scopus 로고
    • For the structural effects on some typical cation solvations, see
    • For the structural effects on some typical cation solvations, see: Arnett, E. M.; Pienta, H. J. J. Am. Chem. Soc. 1980, 102, 3329.
    • (1980) J. Am. Chem. Soc. , vol.102 , pp. 3329
    • Arnett, E.M.1    Pienta, H.J.2
  • 107
    • 0000338757 scopus 로고
    • This analysis implies that the irradiation of the CT band at low temperatures would also afford the ion pair. (See Fukuzumi et al., for such an experimental observation in the CT excitation of analogous EDA complexes
    • This analysis implies that the irradiation of the CT band at low temperatures would also afford the ion pair. (See Fukuzumi et al. [Fukuzumi, S.; Mochida, K.; Kochi, J. K. J. Am. Chem. Soc. 1979, 101, 5961] for such an experimental observation in the CT excitation of analogous EDA complexes.)
    • (1979) J. Am. Chem. Soc. , vol.101 , pp. 5961
    • Fukuzumi, S.1    Mochida, K.2    Kochi, J.K.3
  • 108
    • 2842575309 scopus 로고
    • For questions regarding the solvation of transition states in relation to that of stable molecular analogues, see
    • For questions regarding the solvation of transition states in relation to that of stable molecular analogues, see: Ritchie, C. D. Pure Appl. Chem. 1979, 52, 153.
    • (1979) Pure Appl. Chem. , vol.52 , pp. 153
    • Ritchie, C.D.1
  • 110
    • 0040499323 scopus 로고
    • In this formulation, we do not intend to convey the notion that the configurational structure of the transition state and that of the CT excited ion pair are necessarily the same but only that the energy change in the formation of one serves as a viable model for that of the other. In more rigorous terms, eq 29 states alkenes and arenes are subjected to the same perturbations in electrophilic brominations as in the CT transition in the EDA complexes when changes in solvation are taken into account. It must be emphasized that the CT formulation does not require the proof that an EDA complex is (or is not) an intermediate in electrophilic brominations. For a discussion of this point, see footnotes 19 and 20 in
    • In this formulation, we do not intend to convey the notion that the configurational structure of the transition state and that of the CT excited ion pair are necessarily the same but only that the energy change in the formation of one serves as a viable model for that of the other. In more rigorous terms, eq 29 states alkenes and arenes are subjected to the same perturbations in electrophilic brominations as in the CT transition in the EDA complexes when changes in solvation are taken into account. It must be emphasized that the CT formulation does not require the proof that an EDA complex is (or is not) an intermediate in electrophilic brominations. For a discussion of this point, see footnotes 19 and 20 in: Fukuzumi, S.; Kochi, J. K. J. Am. Chem. Soc. 1980, 102, 2141.
    • (1980) J. Am. Chem. Soc. , vol.102 , pp. 2141
    • Fukuzumi, S.1    Kochi, J.K.2
  • 111
    • 84985521047 scopus 로고
    • The strongest kinetic evidence for the direct involvement of the EDA complex is the observation of a negative temperature coefficient. See
    • The strongest kinetic evidence for the direct involvement of the EDA complex is the observation of a negative temperature coefficient. See: Sergeev, G. B.; Pokolok, T. V.; Ch'eng, T. Kinet. Katal. 1969, 10, 36.
    • (1969) Kinet. Katal. , vol.10 , pp. 36
    • Sergeev, G.B.1    Pokolok, T.V.2    Ch'eng, T.3
  • 120
    • 0003683686 scopus 로고
    • The dielectric constants ϵ are given by:, Chapman, N. B., Shorter, Y., Ed.; Plenum Press: London, Chapter 5
    • The dielectric constants ϵ are given by: Koppel, I. A.; Palm, V. A. “Advances in Linear Free Energy Relationships”; Chapman, N. B., Shorter, Y., Ed.; Plenum Press: London, 1972, Chapter 5.
    • (1972) Advances in Linear Free Energy Relationships
    • Koppel, I.A.1    Palm, V.A.2


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