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Volumn 127, Issue 20, 2005, Pages 7411-7420

Intermolecular electron-transfer mechanisms via quantitative structures and ion-pair equilibria for self-exchange of anionic (dinitrobenzenide) donors

Author keywords

[No Author keywords available]

Indexed keywords

NEGATIVE IONS; POSITIVE IONS; REACTION KINETICS;

EID: 19744373567     PISSN: 00027863     EISSN: None     Source Type: Journal    
DOI: 10.1021/ja051063q     Document Type: Article
Times cited : (28)

References (131)
  • 1
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    • (a) Astruc, D. In Electron Transfer in Chemistry; Balzani, V., Ed.; Wiley-VCH: New York, 2001; Vol. 2, p 714.
    • (2001) Electron Transfer in Chemistry , vol.2 , pp. 714
    • Astruc, D.1
  • 34
    • 19744374032 scopus 로고    scopus 로고
    • note
    • (b) For operational distinction between "separated" and "contact" ion pairs, see footnote 17 in ref 10.
  • 35
    • 19744367245 scopus 로고    scopus 로고
    • note
    • 3a (Vol. 1, p 1 ff).
  • 36
    • 13644249832 scopus 로고    scopus 로고
    • 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.
    • (2005) J. Am. Chem. Soc. , vol.127 , pp. 1797
    • Lü, J.-M.1    Rosokha, S.V.2    Lindeman, S.V.3    Neretin, I.S.4    Kochi, J.K.5
  • 38
    • 19744369575 scopus 로고    scopus 로고
    • note
    • 7
  • 39
    • 19744377617 scopus 로고    scopus 로고
    • note
    • D to that in eq 1a (vide supra).
  • 40
    • 19744368125 scopus 로고    scopus 로고
    • note
    • SEP = -13 eu in Table 1.
  • 41
    • 19744363348 scopus 로고    scopus 로고
    • note
    • 1 (0.35 G) and SIP (0.30 G) owing to the intramolecular spin exchange as described in ref 10.
  • 42
    • 19744368571 scopus 로고    scopus 로고
    • note
    • 10
  • 43
    • 19744365443 scopus 로고    scopus 로고
    • note
    • - in THF and of the free anion in DMF, which are the same,
  • 44
    • 19744375775 scopus 로고    scopus 로고
    • note
    • DA ≥ 6 Å, the counterion effect on dinitrobenzenide reactivity is too small to be evaluated.
  • 45
    • 0043125156 scopus 로고    scopus 로고
    • For some other recent examples of organic mixed-valence systems, see: (a) Lambert, C.; Nöll, G. J. Am. Chem. Soc. 1999, 121, 8434.
    • (1999) J. Am. Chem. Soc. , vol.121 , pp. 8434
    • Lambert, C.1    Nöll, G.2
  • 59
    • 19744363945 scopus 로고    scopus 로고
    • note
    • 6,7
  • 60
    • 19744374211 scopus 로고    scopus 로고
    • note
    • -8 s.
  • 61
    • 19744373937 scopus 로고    scopus 로고
    • note
    • 10
  • 62
    • 19744368240 scopus 로고    scopus 로고
    • note
    • -1.
  • 63
    • 19744372813 scopus 로고    scopus 로고
    • note
    • SIP), and this precludes a more accurate and meaningful analysis.
  • 64
    • 19744363441 scopus 로고    scopus 로고
    • note
    • 2.
  • 65
    • 19744366583 scopus 로고    scopus 로고
    • note
    • a in Table 2, which agree with such a prediction (within the error margins), confirm the validity of this analysis.
  • 72
    • 19744367152 scopus 로고    scopus 로고
    • note
    • 27
  • 73
    • 19744377616 scopus 로고    scopus 로고
    • note
    • 27b
  • 75
    • 19744365049 scopus 로고    scopus 로고
    • note
    • 28b is not expected to contribute to the rate-determining step.
  • 80
    • 19744367244 scopus 로고    scopus 로고
    • note
    • (d) Compare Figure 9b in ref 10.
  • 83
    • 19744367357 scopus 로고    scopus 로고
    • note
    • 25,29 As such, we envisage a wide spectrum of noncovalently bound dyads to encompass the range of adiabatic ET rate processes.
  • 84
    • 19744374773 scopus 로고    scopus 로고
    • 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).
  • 85
    • 0002180347 scopus 로고
    • (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,
    • (1959) Adv. Inorg. Chem. Radiochem. , vol.1 , pp. 1
    • Taube, H.1
  • 87
    • 19744366688 scopus 로고    scopus 로고
    • note
    • 32h
  • 95
    • 19744369746 scopus 로고    scopus 로고
    • 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
  • 97
    • 19744363157 scopus 로고    scopus 로고
    • 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 scopus 로고    scopus 로고
    • note
    • (b) Despite numerous and varied attempts, we have as yet been unable to isolate crystalline K
  • 99
    • 19744367752 scopus 로고    scopus 로고
    • note
    • - associates suitable for X-ray crystallography.
  • 100
    • 19744364563 scopus 로고    scopus 로고
    • note
    • - nor DNB alone absorb there.
  • 103
    • 19744366489 scopus 로고    scopus 로고
    • note
    • DA calculation are given in the Experimental and Computational Methodologies section.
  • 106
    • 19744369267 scopus 로고    scopus 로고
    • note
    • 36b
  • 108
    • 19744365237 scopus 로고    scopus 로고
    • note
    • (c) Also see Brunschwig and Sutin in ref 29.
  • 109
    • 19744365137 scopus 로고    scopus 로고
    • note
    • 32c
  • 110
    • 19744367645 scopus 로고    scopus 로고
    • note
    • -1 range.
  • 114
    • 19744372915 scopus 로고    scopus 로고
    • note
    • -1.
  • 115
    • 19744377615 scopus 로고    scopus 로고
    • note
    • 4a
  • 116
    • 19744378186 scopus 로고    scopus 로고
    • note
    • 4a For equivalency of such an intermolecular precursor complex with electron transfer in bridged mixed-valence systems, see:
  • 118
    • 19744379544 scopus 로고    scopus 로고
    • Sun et al. in ref 33
    • and Sun et al. in ref 33.
  • 119
    • 19744378707 scopus 로고    scopus 로고
    • note
    • -7 s.
  • 120
    • 19744375860 scopus 로고    scopus 로고
    • note
    • -7 s.
  • 121
    • 19744363638 scopus 로고    scopus 로고
    • note
    • 10


* 이 정보는 Elsevier사의 SCOPUS DB에서 KISTI가 분석하여 추출한 것입니다.