Registro:

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• The first spectra of Figures 5 and 6 show a similar dependence on the pH for the intensity and maximum wavelength, at constant R. Now, the maxima are attained at 570 and 535 nm at pH 9.5 and 11.5, respectively; Wilkins, R.G., (1991) Kinetics and Mechanism of Reactions of Transition Metal Complexes, , 2 nd ed., VCH, Weinheim
• The optimal conditions for observing the dependence of D with the pH, for [H+]≤laquo;K2, is R=10, for which D≈k-1. For the highest studied value of R=100, the relative contribution of k -1 to D is nearly 30 %. This fact is in agreement with the reported pH independence when the reaction was studied at R≥100. Thus, the line displayed in Figure 3 was calculated by fitting the data for R=10 and 30; Toma, H.E., Takasugi, M.S., (1983) J. Solution Chem., 12, p. 547
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• The assignment of the reaction in Equation (4) as a spontaneous decomposition of the adduct is supported by our complementary experiments in excess of NP, in which a very similar rate of [Fe(CN)5NO] 3- production has been observed; Das, T.N., Huie, R.E., Neta, P., Padmaja, S., (1999) J. Phys. Chem. A, 103, p. 5221
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• Formation of dominant NH3 and other reduction products (N 2O, NO, NH2OH) in the reactions of free nitrosothiolates with an excess of thiolate allowed proposing diverse structures for the intermediates and their further reactivity modes.[51] We rely on our calculations of the atomic charges for AH, A and a related nitrosothiolate (see Table SI6 in the Supporting Information), revealing that the most positively charged N atom in the Fe-NOS(H) moieties should be the expected site for the nucleophilic attack of HS-. The attack on the S atom of the NOSR group has also been considered for free and protonated nitrosothiolates. [50, 51a]; Miranda, K.M., (2005) Coord. Chem. Rev., 249, p. 433
• Montenegro, A.C., Amorebieta, V.T., Slep, L.D., Martín, D.F., Roncaroli, F., Murgida, D.H., Bari, S.E., Olabe, J.A., (2009) Angew. Chem. Int. Ed., 4823, p. 4213. , the inner-sphere route involving [Fe(CN)5N(OH)(SH) 2]3- appears as more favorable for the formation of [Fe(CN)5NO]4- than the sequential electron transfer implied in the two-electron "outer-sphere" reduction of NP. The second reduction step is a costly process (the half-wave potential is negatively displaced ≈1 V compared to the first one-electron conversion from [Fe(CN)5NO]2- to [Fe(CN)5NO] 3-).[59]
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