SCIENCE CHINA Chemistry. Redox potentials of trifluoromethyl-containing compounds

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1 SCINC CHINA Chemistry SUPPORTING INORMATION doi: /s Redox potentials of trifluoromethyl-containing compounds Yuanye Jiang 1, Haizhu Yu 2,3, Yao u 1* & Lei Liu 3* 1 Department of Chemistry, University of Science and Technology of China, Hefei , China 2 Department of Polymer Science and ngineering, University of Science and Technology Beijing, Beijing , China 3 Department of Chemistry, Tsinghua University, Beijing , China Received March 26, 2014; accepted June 5, 2014; published online October 11, Detail results of ionization potential, electron affinity, bond dissociation enthalpy and redox potentials Table S1 xperimental and calculated ionization potentials and electron affinities of trifluoromethylated and trifluorinated compounds (V) a) xp. B3LYP M06-2X ωb97x-d TPSS mpw1pw9 CAM-B3LY MP2 CH 2 IP CH 2 IP C 3 IP A C 3 C 2 IP A HC 2 C 2 IP C 3 CH IP CH 3 IP B 3 IP P 3 IP R SD RMSD a) xperimental data were taken from the reference: (1) Hollwarth A, Bohme M, Dapprich S, hlers AW, Gobbi A, Jonas V, Kohler K, Stegmann R, Veldkamp A, renking G. A set of d-polarization functions for pseudo-potential basis sets of the main group elements Al Bi and f-type polarization functions for Zn, Cd, Hg. Chem Phys Lett, 1993, 208: ; (2) Trasatti S. The absolute electrode potential: an explanatory note. Pure Appl Chem, 1986, 58: *Corresponding authors ( fuyao@ustc.edu.cn; lliu@mail.tsinghua.edu.cn) Science China Press and Springer-Verlag Berlin Heidelberg 2014 chem.scichina.com link.springer.com

2 2 Jiang et al. Sci China Chem April (2015) Vol.58 No.4 Table S2 xperimental and calculated bond dissociation enthalpy of trifluoromethylated compounds (kcal/mol) a) xp. B3LYP CAM-B3LYP M06-2X B97X-D TPSS mpw1pw ± ± ± ± ± ± ± ± ± ± ± ± ± ± ± ± ± ± ± ± R SD RMSD a) xperimental values are taken from the book: Luo YR. In: Comprehensive Handbook of Chemical Bond nergies. Boca Raton, L: CRC Press, Table S3 xperimental (in V vs aqueous SC) and calculated (in V vs NH) reduction potentials for Test Group 1 Methods C 3 Br C 3 I C 6 13 I R SD Δ1 Δ2 MAD RMSD xp B3LYP CAM-B3LYP M06-2x wb97xd TPSS mpw1pw wb97xd a B3LYP/PCM The redox potentials versus NH were converted to those versus SC by adding a constant of 0.24 V to get the values in Table 2. We note that the test samples in Test Group 1 was too little, we turned to examine the performance of methods on predicting the difference between the measured redox potentials. The reduction potential of C 3 Br minus that of C 3 I to get Δ1, and the reduction potential of C 3 I minus that of C 6 13 I to get Δ2. MAD and RMSD (V) in Table S3 were based on the Δ.

3 Jiang et al. Sci China Chem April (2015) Vol.58 No.4 3 Table S4 xperimental (in V vs Ag/AgCl) and calculated (in V vs NH) redox potentials in CH 2 Cl 2 for Test Group Compouds xp. M06-2X ωb97x-d pc pa pc pa pc pa pc pa pc pa R SD Table S5 The differences between the measured and calculated redox potentials (V) Methods Δ1 Δ2 Δ3 Δ4 Δ5 Δ6 Δ7 Δ8 MAD RMSD xp M06-2X ωb97x-d The redox potentials versus NH were converted to those versus Ag/AgCl by adding a constant of 0.22 V to get the values in Table 3. Δ n (n = 1 4) were the differences between the oxidation peak potentials of compound 2 to 5 and that of compound 1. Δ n (n = 5 8) were the difference between the reduction peak potentials of compound 2 to 5 and that of compound 1. MAD and RMSD (V) were calculated based on the Δ n (n = 1 8). Table S6 Calculated bond dissociation free energy and the bond dissociation enthalpies (BD) from literature of various R-Cl, R-CN and R-C 3 compounds BD from literatures a) Calc. BD 83.7 ± ± ± ± ± ± ± ± ± ± ± ± ± ± ± ± ± (To be continued on the next page)

4 4 Jiang et al. Sci China Chem April (2015) Vol.58 No.4 (Continued) BD from literatures a) Calc. BD ± ± ± ± ± ± ± ± ± ± ± ± ± ± ± ± ± ± ± ± ± ± ± ± ± ± ± ± ± a) These BD values are taken from the book: Luo YR. In: Comprehensive Handbook of Chemical Bond nergies. Boca Raton, L: CRC Press, xamples for redox potential calculation or a better understanding about redox potential calculation, we use three examples including neutral, cationic and anionic species to illustrate it. According to half reactions shown in Scheme 3, the calculations of the redox potential ox-radical, ox-cation, re-radical and re-anion of C 3 CH 3 need to know the free energies of the species C 3 CH 3, C 3, C 3 +, C 3, CH 3 CH 3 + and CH 3 in MeCN. irst, we conduct the geometry optimization of the each individual species with the B97X-D method associated with a moderate basis set (Lanl2dz+p for Br, I and 6-31+G(d) for the rest atoms) in solvent MeCN (solvation model is SMD), to get their stable structures. Based on the optimized structures, frequency analysis is conducted as the same level of theory to obtain the thermodynamic corrections of Gibbs free energies of each species (Table S7). Also, based on the optimized structures, single point energies are calculated to obtain more accurate electronic energies with the B97X-D method associated with a larger basis set (def2-tzvp for Br, I and G(2df,2p) for the rest atoms) in MeCN (solvation model is SMD). Plus the thermodynamic correction and the solution-phase single point energy of each species together to get the solution-phase Gibbs free energy ΔG sol.

5 Jiang et al. Sci China Chem April (2015) Vol.58 No.4 5 Table S7 nergies of some calculated species (Hartree) Thermodynamic corrections to Gibbs free energy Solution-phase single point energies Solution-phase Gibbs free energies C 3 CH C C C CH CH CH According to qs. (1) and (2), we can get the following equations: oxradical 3 3 ΔGsol CH3 ΔGsol C3 ΔGsol C3 CH3 (C CH ) (ev) ΔGsol CH3 ΔGsol C3 ΔGsol C3 CH3 (C CH ) (ev) ΔGsol CH3 ΔGsol C3 ΔGsol C3 CH3 (C CH ) (ev) ΔGsol CH3 ΔGsol C3 ΔGsol C3 CH3 (C CH ) (ev) oxcation 3 3 reradical 3 3 reanion 3 3 where is the conversion factor from Hartree to kcal/mol, is araday constant (23.06 kcal/(mol V)) and 4.44 is the free energy change associated with the reference NH half-reaction (i.e., H + (aq) + e (g) 1/2H 2 (g)). Similarly, the redox potentials ox-radical, ox-cation and re-anion of [C 3 (B 3 )] are calculated by starting from the geometry optimization of the species [C 3 (B 3 )], B 3, B 3 + and B 3 and finally to get their solution-phase Gibbs free energies. Then the redox potentials of [C 3 (B 3 )] are calculated according to the following equations: oxradical 3 3 ΔGsol B3 ΔGsol C3 Δ Gsol [C3 B 3 ] ([C B ] ) (ev) ΔGsol B3 ΔGsol C3 Δ Gsol [C3 B 3 ] ([C B ] ) (ev) ΔGsol B3 ΔGsol C3 Δ Gsol [C3 B 3 ] ([C B ] ) (ev) oxcation 3 3 reanion 3 3

6 6 Jiang et al. Sci China Chem April (2015) Vol.58 No.4 The redox potentials ox-cation, re-radical and re-anion of cationic species [C 3 (NPh 3 )] + can be calculated according the following equations: oxcation 3 3 ΔGsol NPh3 ΔGsol C3 Δ Gsol [C3 NPh 3 ] ([C NPh ] ) (ev) ΔGsol NPh3 ΔGsol C3 Δ Gsol [C3 NPh 3 ] ([C NPh ] (ev) ΔGsol NPh3 ΔGsol C3 Δ Gsol [C3 NPh 3 ] ([C NPh ] (ev) reradical 3 3 reanion Species with high-spin ground state In addition to the energies of the singlet (or doublet) states of all studied species, these of their triplet (or quartet) states are all calculated to find the ground states. These species with triplet (or quartet) states as ground states are shown in Table S8 and the energies of their triplet (or quartet) states were used for redox potential calculations. Note that the geometry optimizations of some high-spin-state species leaded to their decompositions. or example, triplet C 3 SiPh 3 decomposes to [C 3 ] and [SiPh 3 ] after geometry optimization. We did not investigate the redox potentials involving those cases. Table S8 Ground states of calculated compounds Singlet or doublet state Triplet or quartet state Singlet or doublet state Triplet or quartet state NO a) (To be continued on the next page)

7 Jiang et al. Sci China Chem April (2015) Vol.58 No.4 7 (Continued) Singlet or doublet state Triplet or quartet state Singlet or doublet state Triplet or quartet state C 3 S a) means that the species decompose after geometry optimization.

8 8 Jiang et al. Sci China Chem April (2015) Vol.58 No.4 Table S9 Calculated redox potentials of trifluoromethylated radicals ox re ox re NC C C (To be continued on the next page)

9 Jiang et al. Sci China Chem April (2015) Vol.58 No.4 9 (Continued) ox re ox re (To be continued on the next page)

10 10 Jiang et al. Sci China Chem April (2015) Vol.58 No.4 (Continued) ox re ox re N N NH C (To be continued on the next page)

11 Jiang et al. Sci China Chem April (2015) Vol.58 No.4 11 (Continued) ox re ox O O NH C 3 O N H C C O NH

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