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Volumn 125, Issue 28, 2003, Pages 8680-8688

Reversible sequence of intramolecular associative and dissociative electron-transfer reactions in hydrotris(pyrazolylborate) complexes of rhodium

Author keywords

[No Author keywords available]

Indexed keywords

CHARGE TRANSFER; CHEMICAL BONDS; CYCLIC VOLTAMMETRY; ELECTROCHEMISTRY; OXIDATION;

EID: 0038375413     PISSN: 00027863     EISSN: None     Source Type: Journal    
DOI: 10.1021/ja0302073     Document Type: Article
Times cited : (28)

References (91)
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    • (b) ref 1, pp 117-124
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    • There are opposing views on whether the reverse reaction of eq 2 can be considered to be practical under the normal experimental conditions. See refs 2d and 2e for discussion. For theoretical treatment see Saveant, J.-M. J. Electroanal. Chem. 2000, 485, 86.
    • (2000) J. Electroanal. Chem. , vol.485 , pp. 86
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  • 23
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    • Bard, A. J., Ed.; Marcel Dekker: New York
    • For an excellent general review of the square scheme mechanism and the idea of the cross redox reaction, see: (a) Evans, D. H.; O'Connell, K. M. In Electroanalytical Chemistry; Bard, A. J., Ed.; Marcel Dekker: New York, 1986; Vol 14, pp 113 ff. See also: (b) Rieger, P. H. Electrochemistry; Chapman & Hall: New York, 1994; 2nd ed., p 264 and Astruc, D. Electron Transfer and Radical Processes in Transition Metal Chemistry; VCH Publishers: New York, 1995; pp 126-136.
    • (1986) Electroanalytical Chemistry , vol.14
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  • 24
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    • Chapman & Hall: New York, 2nd ed
    • For an excellent general review of the square scheme mechanism and the idea of the cross redox reaction, see: (a) Evans, D. H.; O'Connell, K. M. In Electroanalytical Chemistry; Bard, A. J., Ed.; Marcel Dekker: New York, 1986; Vol 14, pp 113 ff. See also: (b) Rieger, P. H. Electrochemistry; Chapman & Hall: New York, 1994; 2nd ed., p 264 and Astruc, D. Electron Transfer and Radical Processes in Transition Metal Chemistry; VCH Publishers: New York, 1995; pp 126-136.
    • (1994) Electrochemistry , pp. 126-136
    • Rieger, P.H.1
  • 25
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    • VCH Publishers: New York
    • For an excellent general review of the square scheme mechanism and the idea of the cross redox reaction, see: (a) Evans, D. H.; O'Connell, K. M. In Electroanalytical Chemistry; Bard, A. J., Ed.; Marcel Dekker: New York, 1986; Vol 14, pp 113 ff. See also: (b) Rieger, P. H. Electrochemistry; Chapman & Hall: New York, 1994; 2nd ed., p 264 and Astruc, D. Electron Transfer and Radical Processes in Transition Metal Chemistry; VCH Publishers: New York, 1995; pp 126-136.
    • (1995) Electron Transfer and Radical Processes in Transition Metal Chemistry , pp. 126-136
    • Astruc, D.1
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    • (a) Geiger, W. E. Progress in Inorganic Chemistry; Lippard, S. J., Ed.; John Wiley and Sons: New York, 1985; Vol. 33, p 275.
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  • 38
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    • ref 1, pp 111 ff
    • p values are greater than about 200 mV for a one-electron process at 298 K. See (a) ref 1, pp 111 ff. (b) Nicholson, R. S. Anal. Chem. 1965, 37, 1351.
  • 39
    • 33947483336 scopus 로고
    • p values are greater than about 200 mV for a one-electron process at 298 K. See (a) ref 1, pp 111 ff. (b) Nicholson, R. S. Anal. Chem. 1965, 37, 1351.
    • (1965) Anal. Chem. , vol.37 , pp. 1351
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  • 48
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    • Kissinger, P. T., Heineman, W. R., Eds.; Marcel Dekker, New York, 2nd ed
    • Geiger, W. E. In Laboratory Techniques in Electrochemistry; Kissinger, P. T., Heineman, W. R., Eds.; Marcel Dekker: New York, 1996 2nd ed., pp 683 ff.
    • (1996) Laboratory Techniques in Electrochemistry , pp. 683
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  • 49
    • 0037735008 scopus 로고    scopus 로고
    • note
    • 9 is within the sum (2.89 Å) of the van der Waals radius of nitrogen and the atomic radius of rhodium
  • 50
    • 0038411008 scopus 로고    scopus 로고
    • note
    • + is observed under bulk electrolysis conditions at room temperature.
  • 51
    • 0037735007 scopus 로고    scopus 로고
    • note
    • The β parameter is often denoted as 1-α in the literature.
  • 52
    • 0038072574 scopus 로고    scopus 로고
    • note
    • p/2| = 47/β (or α) in mV
  • 53
    • 0037735011 scopus 로고    scopus 로고
    • note
    • For a discussion of transfer coefficients see ref 1, pp 97-98 and ref 8, pp 317-323.
  • 54
    • 0038411018 scopus 로고    scopus 로고
    • note
    • irrev process, chemical intuition and the principle of microscopic reversibility require a coupled chemical reaction in the regeneration of 3.
  • 55
    • 0037735006 scopus 로고    scopus 로고
    • Ref 1, pp 195-197
    • (a) Ref 1, pp 195-197
  • 57
    • 0038072566 scopus 로고    scopus 로고
    • note
    • This designation is intended to bring attention to the two directions of the overall anodic/cathodic process.
  • 60
    • 0038749107 scopus 로고    scopus 로고
    • note
    • s.
  • 61
    • 0038411012 scopus 로고    scopus 로고
    • note
    • 4]. but the main features of the CV remained unchanged.
  • 62
    • 0038411015 scopus 로고    scopus 로고
    • note
    • -1.
  • 63
    • 0038072575 scopus 로고    scopus 로고
    • note
    • p was 90 mV for 1.
  • 64
    • 0038411014 scopus 로고    scopus 로고
    • note
    • p/2 = 38/β mV.
  • 65
    • 0037735009 scopus 로고    scopus 로고
    • note
    • Digital simulations with relatively rapid electron-transfer and chemical follow-up reactions gave reasonable fits with experiment.
  • 69
    • 0038411016 scopus 로고    scopus 로고
    • See ref 1, pp 97-98
    • See ref 1, pp 97-98.
  • 70
    • 0037735004 scopus 로고    scopus 로고
    • note
    • The intermediate (C-type) structures must differ from the B- and A-type structures by more than just the Rh-N(2) bond length, since such a restriction would lead to the unlikely model that the intermediates and products are bond-length isomers. The pseudo square-pyramidal structure avoids this, as would other reasonable structures such as that of the trigonal pyramid.
  • 71
    • 0038411013 scopus 로고    scopus 로고
    • note
    • Data taken from ref 14, from Table 1, and from Yeomans, B., unpublished work.
  • 72
    • 0003049273 scopus 로고
    • The ligand electronic parameters used in Figure 8 are derived from two sources: Rahman, M. M.; Liu, H.-Y.; Eriks, E.; Prock, A.; Giering, W. P. Organometallics, 1989, 8, 1 (b) Chatt, J.; Kan, C. T.; Leigh, G. J.; Pickett, C. J.; Stanley, D. R. J. Chem. Soc., Dalton Trans. 1980, 2032. See also Lever, B. Inorg. Chem. 1990, 29, 1271, and references therein.
    • (1989) Organometallics , vol.8 , pp. 1
    • Rahman, M.M.1    Liu, H.-Y.2    Eriks, E.3    Prock, A.4    Giering, W.P.5
  • 73
    • 37049095226 scopus 로고
    • The ligand electronic parameters used in Figure 8 are derived from two sources: Rahman, M. M.; Liu, H.-Y.; Eriks, E.; Prock, A.; Giering, W. P. Organometallics, 1989, 8, 1 (b) Chatt, J.; Kan, C. T.; Leigh, G. J.; Pickett, C. J.; Stanley, D. R. J. Chem. Soc., Dalton Trans. 1980, 2032. See also Lever, B. Inorg. Chem. 1990, 29, 1271, and references therein.
    • (1980) J. Chem. Soc., Dalton Trans. , pp. 2032
    • Chatt, J.1    Kan, C.T.2    Leigh, G.J.3    Pickett, C.J.4    Stanley, D.R.5
  • 74
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    • and references therein
    • The ligand electronic parameters used in Figure 8 are derived from two sources: Rahman, M. M.; Liu, H.-Y.; Eriks, E.; Prock, A.; Giering, W. P. Organometallics, 1989, 8, 1 (b) Chatt, J.; Kan, C. T.; Leigh, G. J.; Pickett, C. J.; Stanley, D. R. J. Chem. Soc., Dalton Trans. 1980, 2032. See also Lever, B. Inorg. Chem. 1990, 29, 1271, and references therein.
    • (1990) Inorg. Chem. , vol.29 , pp. 1271
    • Lever, B.1
  • 75
    • 0037735010 scopus 로고    scopus 로고
    • note
    • We invoke the general principle of microscopic reversibility.
  • 84
    • 0038411007 scopus 로고    scopus 로고
    • note
    • Entries a-d of ref 47 refer to net two-electron processes.


* 이 정보는 Elsevier사의 SCOPUS DB에서 KISTI가 분석하여 추출한 것입니다.