Analysis of the substituent effect on the reactivity modulation during self-protonation processes in 2-nitrophenols.

A voltammetric and spectroelectrochemical ESR study of the reduction processes of five substituted 4-R-2-nitrophenols (R = -H, -OCH(3), -CH(3), -CN, -CF(3)) in acetonitrile was performed. In the potential range considered here (-0.2 to -2.5 V vs Fc+/Fc), two reduction signals (Ic and IIc) were detected; the first one was associated with the formation of the corresponding hydroxylamine via a self-protonation pathway. The voltammetric analysis at the first reduction signal showed that there are differences in the reduction pathway for each substituted 4-R-2-nitrophenol, being the E1/2 values determined by the inductive effect of the substituent in the meta position with respect to the nitro group, while the electron-transfer kinetics was determined by the protonation rate (k(1)+ ) of the anion radical electrogenerated. However, at potential values near the first reduction peak, no ESR signal was recorded from stable radical species, indicating the instability of the radical species in solution. Nevertheless, an intense ESR spectrum generated at the second reduction peak was detected for all compounds, indicating the monoelectronic reduction of the corresponding deprotonated 4-R-2-nitrophenols. The spin-coupling hyperfine structures revealed differences in the chemical nature of the electrogenerated radical; meanwhile, the -CF(3) and -CN substituents induced the formation of a dianion radical structure, and the -H, -CH(3), and -OCH(3) substituents provoked the formation of an anion radical structure due to protonation by acetonitrile molecules of the initially electrogenerated dianion radical. This behavior was confirmed by analyzing the ESR spectra in deuterated acetonitrile and by performing quantum chemical calculations of the spin densities at each site of the electrogenerated anionic radicals.

Remote position substituents as modulators of conformational and reactive properties of quinones. Relevance of the pi/pi intramolecular interaction.

Several studies have described that quinoid rings with electron-rich olefins at remote position experience changes in their redox potential. Since the original description of these changes, different approaches have been developed to describe the properties of the binding sites of ubiquinones. The origin of this phenomenon has been attributed to lateral chain flexibility and its effect on the recognition between proteins and substrates associated with their important biological activity. The use of electrochemical-electron spin resonance (EC-ESR) assays and theoretical calculations at MP2/6-31G(d,p) and MP2/6-31++G(d,p)//MP2/6-31G(d,p) levels of several conformers of perezone [(2-(1,5-dimethyl-4-hexenyl)-3-hydroxy-5-methyl-1,4-benzoquinone] established that a weak pi-pi interaction controls not only the molecular conformation but also its diffusion coefficient and electrochemical properties. An analogous interaction can be suggested as the origin of similar properties of ubiquinone Q10. The use of nuclear magnetic resonance rendered, for the first time, direct evidence of the participation of different perezone conformers in solution and explained the cycloaddition process observed when the aforementioned quinone is heated to form pipitzols, sesquiterpenes with a cedrene skeleton. The fact that biological systems can modulate the redox potential of this type of quinones depending on the conformer recognized by an enzyme during a biological transformation is of great relevance.