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Throughout the present paper, P designates the π-rings of the porphyrins. The dot designates an electron delocalized over the two π-rings, and the three dashes are the equivalent of a weak π-π bond obtained by pairing of two electrons (see ref 17). In the following the formal redox states of the cobalt will be omitted unless the issue of the electron repartition is specifically addressed.
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17,18 we designate (i) by process the global abstraction of two electrons from the dimer, corresponding to one electron for each monomeric unit constituting the dimer, and (ii) by step each of the individual electrochemical reactions. Each process can thus take place either in two one-electron steps or in one two-electron step, not excluding that they may be intermingled.
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(c) Scheme 1 corresponds almost exactly to that proposed by Savéant et al. from similar observations as a model example. Thermodynamic treatment for the determination of the constants was made following the same procedure. Lexa, D.; Rentien, P.; Savéant, J. M.; Xu, F. J. Electroanal. Chem. 1985, 191, 253.
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46549098867
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max of the Soret band of the oxy form of the complexes (400-410 nm range), where the absorbance variations are maximal. The data were computed with the "Micmac" program for nonlinear least-squares multiparametric refinement of Laouenan et al., which allows the direct determination of the equilibrium constants. See: Laouénan, A.; Suet, E. Talanta 1985, 32, 245.
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16944367305
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note
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O2(2) are constant within this range, and the averages are presented in Table 2.
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78
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16944365960
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note
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16 and consequently the observation of isosbestic sets of spectra.
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79
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16944366107
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Solomon, E. I.; Hemming, B. L.; Root, D. E. In ref 12a
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16944366622
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Tyeklár, Z.; Karlin, K. D. Ibid
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16944366539
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(e) The compound of Kitajima et al. has been found to model accurately the structure of the Limulus polyphemus oxyhemocyanin reported sometime later:
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16944366311
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note
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11
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105
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0029349854
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Mahapatra, S.; Halfen, J. A.; Wilkinson, E. C.; Pan, G.; Cramer, C. J.; Que, L. Jr.; Tolman, W. B. J. Am. Chem. Soc. 1995, 117, 8865.
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Tolman, W.B.7
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106
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16944365693
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note
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3
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107
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0001125155
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Guilard, R.; Brandès, S.; Tardieux, C.; Tabard, A.; L'Her, M.; Miry, C.; Gouerec, P.; Knop, Y.; Collman, J. P. J. Am Chem. Soc. 1995, 117, 11721.
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Guilard, R.1
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Miry, C.6
Gouerec, P.7
Knop, Y.8
Collman, J.P.9
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108
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16944366189
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note
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2 complexes would require a higher level of theory. Such calculations are in progress.
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