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to attack and capture CO . 2 6 Cu −1.80 78 2 3.3. Electrocarboxylation of Cyano-Compounds 6 and 7 under CO2 Atmposphere According to previous results obtained in our research group[151], 4-iodobenzonitrile follows an ECE reduction mechanism in ionic liquids (Scheme 6). In the presence of CO2 the electrogenerated C 2020, 6, 34 11 of 21 anion intermediate leads to the corresponding carboxylation process. Hence, with the aim to obtain a stronger electrogenerated nucleophile, R− (Scheme 6), we decided to move from nitro to cyano aromatic compounds. Thus, two new different p-cyanobenzene halides (4-chlorobenzonitrile (6) and aromatic compounds. Thus, two new different p-cyanobenzene halides (4-chlorobenzonitrile (6) and 4-bromobenzonitrile (7)) were explored in this section. 4-bromobenzonitrile (7)) were explored in this section. Scheme 6. General overview for an ECE electrocarboxylation mechanism. Scheme 6. General overview for an ECE electrocarboxylation mechanism. Figure 5 shows CVs at DMF/0.1M TBA BF and one example in EMIM TFSI obtained under Figure 5 shows CVs at DMF/0.1M TBA BF4 a4nd one example in EMIM TFSI obtained under inert inert atmosphere and CO atmosphere. All electrochemical parameters are summarized in Table 4. atmosphere and CO2 atm2osphere. All electrochemical parameters are summarized in Table 4. The The same general trend was observed in aprotic solvents and ionic liquids. Moreover, not significate same general trend was observed in aprotic solvents and ionic liquids. Moreover, not significate differences were detected when the nature of the working electrode was changed. differences were detected when the nature of the working electrode was changed. As it was expected compounds 6 and 7 exhibit an irreversible bielectronic wave under nitrogen atmosphere for any of the working electrodes investigated (Figure 5a,b). The same electrochemical behavior is observed when DMF is replaced by EMIM TFSI. A closer look to cyclic voltammograms reveals the electrocatalytic properties of silver as a working electrode, since the peak potential value of the reduction peak is shifted to less negative potentials. In order to determine the nature of the product formed upon reduction, a controlled potential electrolysis was performed. In all the cases benzonitrile, 8, was the only product obtained after the passage of 2F. Taking into account CVs and the electrochemical data obtained from the electrolysis, it is possible to conclude that compound 6 and 7 follows an ECE mechanism. In a first electrochemical step, the radical anion of benzonitrile halide was generated. After that, a chemical reaction coupled to this first electron transfer led to a benzonitrile radical and the corresponding halide anion through a C-X cleavage reaction. Later, benzonitrile radical was reduced to its corresponding anion at the electrode surface (Scheme 7). It is important to remark that when cyano derivatives are used, it is possible to electrogenerate a strong nucleophile (benzonitrile anion), which is stable enough under our experimental conditions for reacting with CO2 leading to the C 2020, 6, x FOR PEER REVIEW 12 of 21 corresponding electrocarboxylated product. Figure 5. Cyclic voltammetry of 10 mM p-cyano compounds 6 and 7 in DMF/0.1M TBA BF4 with Ag Figure 5. Cyclic voltammetry of 10 mM p-cyano compounds 6 and 7 in DMF/0.1M TBA BF4 with Ag (black line), Cu (red line) and C (blue line), under inert atmosphere (left) and CO atmosphere (right). (black line), Cu (red line) and C (blue line), under inert atmosphere (left) and CO22atmosphere (right). −1 −1 Scanrate:0.S5caVn·srate.:0.5V·s . Table 4. Electrochemical parameters for electroreduction of compounds 6 and 7 in DMF/0.1M TBA BF4 and EMIM TFSI. DMF/0.1M TBA BF4 Entries Cyano Derivative WE Epc (V vs. SHE) ΔEp (mV) 1 Ag −1.73 85PDF Image | Electrochemical Tuning of CO2 Reactivity in Ionic Liquids
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