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36849118220
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0010591540
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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.
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-
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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
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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.
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Masuhara, H.1
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33847089778
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k(DA*) in eq a and b is unlikely for weak complexes. For the nature of in molecular complexes, see
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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.]
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2742611721
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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;
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85088543834
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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.
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21944431525
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−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;
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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.
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Reynolds, W.L.1
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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
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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.
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For typical products of 1-equiv oxidation of aromatic compounds, see the reviews by
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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.
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84985415729
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This follows from the general form of the free energy relationship applicable to the endergonic region, see:, See also ref 34
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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.
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Agmon, N.1
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0012566066
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The solvation of the neutral species is neglected in comparison with that of the donor cation
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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.
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Lofti, M.1
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0001589004
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It is also assumed that the vertical and adiabatic cations have essentially the same structure. However, see
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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.
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85021562602
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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.
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Case, B.1
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0000254205
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Latimer, W. M.; Pitzer, K. S.; Slansky, C. M. J. Chem. Phys. 1939, 7, 108.
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0038619561
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For the structural effects on some typical cation solvations, see
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For the structural effects on some typical cation solvations, see: Arnett, E. M.; Pienta, H. J. J. Am. Chem. Soc. 1980, 102, 3329.
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33947093182
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for leading references
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107
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0000338757
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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.)
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2842575309
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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.
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0040499323
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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.
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84985521047
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The strongest kinetic evidence for the direct involvement of the EDA complex is the observation of a negative temperature coefficient. See
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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.
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85021538362
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Briggs, D., Ed.; Clowes: London, Chapter 10
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Thompson, M.; Hewitt, P. A.; Wooliscroft, D. S. In “Handbook of X-ray and Ultraviolet Photoelectron Spectroscopy”; Briggs, D., Ed.; Clowes: London, 1978; Chapter 10, p 344.
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0003683686
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The dielectric constants ϵ are given by:, Chapman, N. B., Shorter, Y., Ed.; Plenum Press: London, Chapter 5
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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.
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Koppel, I.A.1
Palm, V.A.2
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