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24 The structural change must be reversible to account for the overall electrochemical reversibility that is observed.
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For very large distortions of the positive ion away from the vibrational amplitudes of the neutral molecule, adiabatic ionization intensity may not be observed and the onset of ionization intensity represents an upper bound to the true adiabatic ionization energy
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For very large distortions of the positive ion away from the vibrational amplitudes of the neutral molecule, adiabatic ionization intensity may not be observed and the onset of ionization intensity represents an upper bound to the true adiabatic ionization energy.
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Although calculations show that reaction of 6H2- with AcOH is facile, it has been reported that a μ-H in a Fe-only hydrogenase model with two Fe(II) centers is experimentally unreactive to HOTf or H(OEt 2)2BArF4 in contrast to its terminal hydride isomer: van der Vlugt, J. I, Rauchfuss, T. B, Whaley, C. M, Wilson, S. R. J. Am. Chem. Soc. 2005, 127, 16012-16013
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Compound 6 is not stable in the presence of acetate alone with decomposition occurring over a period of a few minutes. The presence of acid slows the decomposition. The data shown in Figure 4 were obtained by adding 10 mM acetic acid to the solution containing 0.100 M acetate. Then the catalyst was added, and the voltammogram was recorded. The acetic acid concentration was then increased to 50 mM. We suspect that the smaller peak height for catalyst reduction seen with 50 mM is due to some decomposition that occurred between recording the 10 and 50 mM voltammograms
-
Compound 6 is not stable in the presence of acetate alone with decomposition occurring over a period of a few minutes. The presence of acid slows the decomposition. The data shown in Figure 4 were obtained by adding 10 mM acetic acid to the solution containing 0.100 M acetate. Then the catalyst was added, and the voltammogram was recorded. The acetic acid concentration was then increased to 50 mM. We suspect that the smaller peak height for catalyst reduction seen with 50 mM is due to some decomposition that occurred between recording the 10 and 50 mM voltammograms.
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The results of simulations reported in Figure 5 are for the catalytic peak current only. As seen in Figure 6, another feature of the data is that the peak potential moves in the positive direction as the acid strength increases. The simulated peak potentials, however, are almost independent of acid strength, based on reactions 3 through 8. There are various other reactions that will cause a potential shift similar to that seen in Figure 6. For example, formation of a hydrogen-bonded complex between 6H- and A, 6H-·A, or between 6H2- and HA (6H2--HA) will have the effect of shifting the peak if one assumes that the formation constants correlate with acid strength. As there are many such possible reactions, and perhaps other types as well, we have refrained from attempting to fit this potential shift
-
2--HA) will have the effect of shifting the peak if one assumes that the formation constants correlate with acid strength. As there are many such possible reactions, and perhaps other types as well, we have refrained from attempting to fit this potential shift.
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