Table 2 Electrochemical properties of selected solvents S and redox active species therein

From: Pushing redox potentials to highly positive values using inert fluorobenzenes and weakly coordinating anions

Solvent S	E_neg	E_pos	ECW	IE / eV	E_1/2(NO⁺(S)/NO)	E°´ (Ag⁺(S)/Ag)
1FB	−3.18	+1.82	5.00	9.20⁶⁸	+1.11	+0.74
2FB	−3.09	+2.05	5.14	9.29⁶⁸	+1.23	+0.99
3FB	−3.02	+2.35	5.37	9.40¹¹⁸	+1.42	+1.26
4FB	−3.08	+2.43	5.51	9.53⁶⁸	+1.52	+1.47
5FB	−2.37	+2.67	5.04	9.63⁶⁸	+1.47 (+1.47 with [al-f-al]⁻)	+1.50
CH₂Cl₂	−2.91 (−2.62^a)	+3.36 (+2.58^a)	6.27 (5.20^a)	11.33^b	+1.40 [+1.00^c,d] (+0.95^e)	+0.88 [+0.65^d]
1,2-Cl₂C₂H₄	−2.28	+3.13	5.41	11.07^b	+1.23	+0.66
DMF	−3.60	+1.73	5.33	9.13^b	+0.54 [+0.56^c]	+0.11 [+0.49^c,f]
AN	−3.09	+4.59	7.68	12.20^b	+0.87 [+0.87^c]	+0.02 [+0.06^g]
PC	−3.50	+4.15	7.65	(10.5)^b,c
THF	−3.60	+1.33	4.93	9.40^b

Negative reduction E_neg, positive oxidation E_pos limits and derived potential windows of stability (ECW) were derived from CV measurements of the selected solvents at v = 100 mV s⁻¹ with 100 mm [NBu₄]⁺[pf]⁻ as supporting electrolyte in S, if not stated otherwise. For comparison, the Ionization Energies IE of the solvents are included. Cyclovoltammetrically determined potential values of the redox systems Ag⁺(S)/Ag and NO⁺(S)/NO, with S as xFB (x = 1–5) or other solvents are given. The CVs were obtained with Pt disc electrodes, the used counterion was [pf]⁻, the supporting electrolyte was 100 mm [NBu₄]⁺[pf]⁻, the scan rate was varied between 20 and 200 mV s⁻¹, but E_1/2 is independent of the rate. Literature values are given in square brackets in italics where available, own control experiments with alternative reagents are given in parentheses in regular font. All potential values are given in V with reference to E°´((Fc⁺/Fc) S) with an uncertainty of ±0.025 V. All measurement data are given in the Supplementary Information (xFB: NO⁺/NO Supplementary Notes 3.4.1 (with respect to Fc⁺/Fc) and 3.5.2 (with respect to Ag⁺/Ag); Ag⁺/Ag Supplementary Note 3.5.1. Other solvents: NO⁺/NO Supplementary Note (with respect to Fc⁺/Fc) and 3.7.2 (with respect to Ag⁺/Ag); Ag⁺/Ag Supplementary Note 3.7.1).
^a[NBu₄]⁺[PF₆]⁻ as conducting salt.
^bNIST Chemistry Webbook https://webbook.nist.gov/chemistry/.
^cAppearance energy from ^b. Values from the literature⁵.
^dFrom the literature^5,19, using Ag⁺[PF₆]⁻ with [NBu₄]⁺[PF₆]⁻ and NO⁺[BF₄]⁻ with [NBu₄]⁺[BF₄]⁻ as supporting electrolyte.
^eIndependent own control measurement in CH₂Cl₂ using 10 mm NO⁺[PF₆]⁻ with 100 mm [NBu₄]⁺[PF₆]⁻ as supporting electrolyte (See Supplementary Note 3.6.1.3).
^fThis potential was given as an estimate in ref. ⁵ and appears to be completely wrong. Our value is confirmed in the triangular evaluation in Supplementary Note 3.7.3.
^gValue from the literature²¹.

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Table 2 Electrochemical properties of selected solvents S and redox active species therein

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