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34
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19744374032
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note
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(b) For operational distinction between "separated" and "contact" ion pairs, see footnote 17 in ref 10.
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35
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19744367245
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note
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3a (Vol. 1, p 1 ff).
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36
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13644249832
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Lü, J.-M; Rosokha, S. V.; Lindeman, S. V.; Neretin, I. S.; Kochi, J. K. J. Am. Chem. Soc. 2005, 127, 1797. The X-ray structure below illustrates how the interionic separation in the separated ion pair is enforced via complete encapsulation of potassium so that the cation is effectively insulated from the dinitrobenzenide counteranion by the wide interionic separation of ≥6 Å.
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Lü, J.-M.1
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Kochi, J.K.5
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37
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0141919820
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Nelsen, S. F.; Konradsson, A. E.; Weaver, M. N.; Telo, J. P. J. Am. Chem. Soc. 2003, 125, 12493.
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Nelsen, S.F.1
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Weaver, M.N.3
Telo, J.P.4
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38
-
-
19744369575
-
-
note
-
7
-
-
-
-
39
-
-
19744377617
-
-
note
-
D to that in eq 1a (vide supra).
-
-
-
-
40
-
-
19744368125
-
-
note
-
SEP = -13 eu in Table 1.
-
-
-
-
41
-
-
19744363348
-
-
note
-
1 (0.35 G) and SIP (0.30 G) owing to the intramolecular spin exchange as described in ref 10.
-
-
-
-
42
-
-
19744368571
-
-
note
-
10
-
-
-
-
43
-
-
19744365443
-
-
note
-
- in THF and of the free anion in DMF, which are the same,
-
-
-
-
44
-
-
19744375775
-
-
note
-
DA ≥ 6 Å, the counterion effect on dinitrobenzenide reactivity is too small to be evaluated.
-
-
-
-
45
-
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0043125156
-
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For some other recent examples of organic mixed-valence systems, see: (a) Lambert, C.; Nöll, G. J. Am. Chem. Soc. 1999, 121, 8434.
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Lambert, C.1
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0037242057
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(c) Risko, C.; Barlow, S.; Coropceanu, V.; Halik, M.; Bredas, J.-L.; Marder, S. R. Chem. Commun. 2003, 194.
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Risko, C.1
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48
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0037028565
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(d) Lindeman, S. V.; Rosokha; S. V.; Sun, D.-L.; Kochi, J. K. J. Am. Chem. Soc, 2002, 124, 843.
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Lindeman, S.V.1
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51
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36849107663
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(a) Miller, T. A.; Adams, R. N.; Richards, P. M. J. Chem. Phys. 1966, 44, 4022.
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Miller, T.A.1
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52
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19744374210
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See also: (b) Layoff, T.; Miller, T. A.; Adams, R. N.; Fah, H.; Horsfield, A.; Proctor, W. Nature 1965, 205, 4969.
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59
-
-
19744363945
-
-
note
-
6,7
-
-
-
-
60
-
-
19744374211
-
-
note
-
-8 s.
-
-
-
-
61
-
-
19744373937
-
-
note
-
10
-
-
-
-
62
-
-
19744368240
-
-
note
-
-1.
-
-
-
-
63
-
-
19744372813
-
-
note
-
SIP), and this precludes a more accurate and meaningful analysis.
-
-
-
-
64
-
-
19744363441
-
-
note
-
2.
-
-
-
-
65
-
-
19744366583
-
-
note
-
a in Table 2, which agree with such a prediction (within the error margins), confirm the validity of this analysis.
-
-
-
-
72
-
-
19744367152
-
-
note
-
27
-
-
-
-
73
-
-
19744377616
-
-
note
-
27b
-
-
-
-
75
-
-
19744365049
-
-
note
-
28b is not expected to contribute to the rate-determining step.
-
-
-
-
79
-
-
0000486587
-
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Balzani, V., Ed.; Wiley: New York
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(c) Brunschwig, B. S.; Sutin, N. In Electron Transfer in Chemistry; Balzani, V., Ed.; Wiley: New York, 2001; Vol. 2, p 583.
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Brunschwig, B.S.1
Sutin, N.2
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80
-
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19744367244
-
-
note
-
(d) Compare Figure 9b in ref 10.
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81
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84962339703
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(a) Vener, M. V.; Ioffe, N. T.; Cheprakov, A. V.; Mairanovsky, V. G. J. Electroanal. Chem. 1994, 370, 33.
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83
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19744367357
-
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note
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25,29 As such, we envisage a wide spectrum of noncovalently bound dyads to encompass the range of adiabatic ET rate processes.
-
-
-
-
84
-
-
19744374773
-
-
note
-
o via the Kirkwood model, which relates the solvent reorganization energy for the charge redistribution accompanying electron transfer within the precursor complex (considered as a single entity surrounded by the polarizable medium).
-
-
-
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85
-
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0002180347
-
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(b) We relate inner-sphere complexes in organic redox systems (of the type described herein) to the direct overlap of donor/acceptor orbitals without the intervention of solvent, in harmony with the classical description of inner-sphere complexes in inorganic systems that involve metal centers bridged by ligands in the first coordination sphere. See, for example: Taube, H. Adv. Inorg. Chem. Radiochem. 1959, 1, 1,
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note
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32h
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88
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(d) Nagayoshi, K.; Kabir, M. K.; Tobita, H.; Honda, K.; Kawahara, M.; Katada, M.; Adachi, K.; Nishikawa, H.; Ikemoto, I.; Kumagai, H.; Hosokoshi, Y.; Inoue, K.; Kitagawa, S.; Kawata, S. J. Am. Chem. Soc. 2003, 125, 221.
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19744369746
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Ganesan et al. in ref 32c
-
For the role of such precursor complexes in the quantitative kinetics for other electron-transfer self-exchanges, see (a) Ganesan et al. in ref 32c
-
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96
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1042288185
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and (b) Sun, D. L.; Rosokha, S. V.; Kochi, J. K. J. Am. Chem. Soc. 2004, 126, 1388.
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97
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19744363157
-
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note
-
DA = 3.3 and 3.8 Å as well as those with "slipped" and rotated DNB moieties were also considered as discussed in the Experimental and Computational Methodologies section.
-
-
-
-
98
-
-
19744367924
-
-
note
-
(b) Despite numerous and varied attempts, we have as yet been unable to isolate crystalline K
-
-
-
-
99
-
-
19744367752
-
-
note
-
- associates suitable for X-ray crystallography.
-
-
-
-
100
-
-
19744364563
-
-
note
-
- nor DNB alone absorb there.
-
-
-
-
103
-
-
19744366489
-
-
note
-
DA calculation are given in the Experimental and Computational Methodologies section.
-
-
-
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105
-
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20644436909
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(b) Blomgren, F.; Larsson, S.; Nelsen, S. F. J. Comput. Chem. 2001, 22, 655.
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Blomgren, F.1
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106
-
-
19744369267
-
-
note
-
36b
-
-
-
-
108
-
-
19744365237
-
-
note
-
(c) Also see Brunschwig and Sutin in ref 29.
-
-
-
-
109
-
-
19744365137
-
-
note
-
32c
-
-
-
-
110
-
-
19744367645
-
-
note
-
-1 range.
-
-
-
-
114
-
-
19744372915
-
-
note
-
-1.
-
-
-
-
115
-
-
19744377615
-
-
note
-
4a
-
-
-
-
116
-
-
19744378186
-
-
note
-
4a For equivalency of such an intermolecular precursor complex with electron transfer in bridged mixed-valence systems, see:
-
-
-
-
117
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0346994916
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(c) Sun, D. L.; Rosokha, S. V.; Lindeman, S. V.; Kochi, J. K. J. Am. Chem. Soc. 2003, 125, 15950
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118
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19744379544
-
-
Sun et al. in ref 33
-
and Sun et al. in ref 33.
-
-
-
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119
-
-
19744378707
-
-
note
-
-7 s.
-
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-
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120
-
-
19744375860
-
-
note
-
-7 s.
-
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-
-
121
-
-
19744363638
-
-
note
-
10
-
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124
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