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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.
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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.
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Stoll, M. E.; Belanzoni, P.; Calhorda, M. J.; Drew, M. G. B.; Felix, V.; Geiger, W. E.; Gamelas, C. A.; Gonçalves, I. S.; Româo, C. C.; Veiros, L. F. J. Am. Chem. Soc. 2001, 123, 10 595, and references therein.
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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.
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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.
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Geiger, W.E.1
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49
-
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0037735008
-
-
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
-
-
note
-
+ is observed under bulk electrolysis conditions at room temperature.
-
-
-
-
51
-
-
0037735007
-
-
note
-
The β parameter is often denoted as 1-α in the literature.
-
-
-
-
52
-
-
0038072574
-
-
note
-
p/2| = 47/β (or α) in mV
-
-
-
-
53
-
-
0037735011
-
-
note
-
For a discussion of transfer coefficients see ref 1, pp 97-98 and ref 8, pp 317-323.
-
-
-
-
54
-
-
0038411018
-
-
note
-
irrev process, chemical intuition and the principle of microscopic reversibility require a coupled chemical reaction in the regeneration of 3.
-
-
-
-
55
-
-
0037735006
-
-
Ref 1, pp 195-197
-
(a) Ref 1, pp 195-197
-
-
-
-
57
-
-
0038072566
-
-
note
-
This designation is intended to bring attention to the two directions of the overall anodic/cathodic process.
-
-
-
-
58
-
-
0035926237
-
-
3CN (Davison, A.; Edelstein, N.; Holm, R. H.; Maki, A. H. Inorg. Chem. 1963, 2, 1227.
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Geiger, W.E.1
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59
-
-
33947478566
-
-
3CN (Davison, A.; Edelstein, N.; Holm, R. H.; Maki, A. H. Inorg. Chem. 1963, 2, 1227.
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-
Davison, A.1
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Maki, A.H.4
-
60
-
-
0038749107
-
-
note
-
s.
-
-
-
-
61
-
-
0038411012
-
-
note
-
4]. but the main features of the CV remained unchanged.
-
-
-
-
62
-
-
0038411015
-
-
note
-
-1.
-
-
-
-
63
-
-
0038072575
-
-
note
-
p was 90 mV for 1.
-
-
-
-
64
-
-
0038411014
-
-
note
-
p/2 = 38/β mV.
-
-
-
-
65
-
-
0037735009
-
-
note
-
Digital simulations with relatively rapid electron-transfer and chemical follow-up reactions gave reasonable fits with experiment.
-
-
-
-
69
-
-
0038411016
-
-
See ref 1, pp 97-98
-
See ref 1, pp 97-98.
-
-
-
-
70
-
-
0037735004
-
-
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
-
-
note
-
Data taken from ref 14, from Table 1, and from Yeomans, B., unpublished work.
-
-
-
-
72
-
-
0003049273
-
-
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.
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73
-
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37049095226
-
-
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.
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74
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33751553266
-
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and references therein
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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.
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We invoke the general principle of microscopic reversibility.
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78
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37049094727
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15844385775
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84
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0038411007
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note
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Entries a-d of ref 47 refer to net two-electron processes.
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86
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0029975355
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(b) Delville-Desbois, M.-H.; Mross, S.; Astruc, D.; Linares, J.; Varret, F.; Rabaâ; Le Beuze, A.; Saillard, J.-Y.; Culp R. D.; Atwood, D. A.; Cowley, A. H. J. Am. Chem. Soc. 1996, 118, 4133.
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Le Beuze, A.7
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Atwood, D.A.10
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33845278135
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