"Unique Ligand Radical Character of an Activated Cobalt Salen Catalyst that is Generated. Takuya Kurahashi and Hiroshi Fujii *

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1 Supporting Information for "Unique Ligand Radical Character of an Activated Cobalt Salen Catalyst that is Generated by Aerobic Oxidation of a Cobalt(II) Salen Complex" Takuya Kurahashi and Hiroshi Fujii * Institute for Molecular Science & Okazaki Institute for Integrative Bioscience, National Institutes of Natural Sciences, Myodaiji, Okazaki, Aichi , Japan * To whom correspondence should be addressed. hiro@ims.ac.jp

2 Figure S1. Cyclic voltammograms of (a) Co(L-OMe)(OTf), (b) Co(L-t-Bu)(OTf), (c) Co(L-Cl)(OTf) (d) Co(L-OMe/t-Bu)(OTf) (e) Co(L-OMe/Cl)(OTf) in CH 2 Cl 2 at 233 K. Conditions: 1 mm, 0.1 M of Bu 4 NOTf supporting electrolyte, a saturated calomel electrode as reference electrode, a glassy-carbon working-electrode, a platinum-wire counter electrode, a scan rate of 50 mv s 1. The potentials are referenced versus the ferrocenium/ferrocene couple (Fc + /Fc). S 1

3 Table S1. Crystallographic data for Co(L-OMe)(OTf). Co(L-OMe)(OTf) formula C 62 H 80 F 6 Co 2 N 4 O 14 S 2 Mr T / C 180 cryst size / mm cryst system monoclinic space group P2 1 (No. 4) cryst color brown a / Å (5) b / Å (5) c / Å (10) α / deg β / deg (7) γ / deg V / Å (2) Z value 2 D calc /g cm GOF R1 a R w b Flack 0.05(3) a R1 = F o F c / F o b R w = [ w(f o 2 F c 2 ) 2 / w(f o 2 ) 2 ] 1/2 S 2

4 Figure S2. Packing diagram of Co(L-OMe)(OTf) molecules a and b in the asymmetric cell. S 3

5 Figure S3. Differences of the structural parameters between Co(L-OMe)(OTf) and Co II (L-OMe). The charts show increased (red bar) or decreased (blue bar) bond length of left and right phenolates of Co(L-OMe)(OTf) (molecule a and b, Figure 1), as compared with the averaged bond length of left and right phenolates of Co II (L-OMe). The structural parameters of Co II (L-OMe) are adopted from the following reference; Kochem, A.; Kanso, H.; Baptiste, B.; Arora, H.; Philouze, C.; Jarjayes, O.; Vezin, H.; Luneau, D.; Orio, M.; Thomas, F. Inorg. Chem. 2012, 51, S 4

6 Figure S4. 1 H NMR spectrum of 20 mm solution of Co III (L-t-Bu)(OAc) in CD 2 Cl 2 at 298 K. S 5

7 Figure S5. Co L-edge X-ray absorption spectra of Co(L-OMe)(OTf) (red line), Co II (L-OMe) (blue line), and Co III (L-t-Bu)(OAc) (black line). S 6

8 Figure S6. Co L-edge X-ray absorption spectra of Co II (NO 3 ) 2 (H 2 O) 6 (blue line) and [Co III (NH 3 ) 6 ]Cl 3 (red line). S 7

9 Figure S7. Co L-edge X-ray absorption spectra of (a) Co II (L-OMe), (b) Co(L-OMe)(OTf), and (c) Co III (L-t-Bu)(OAc) before (black line) and after X-ray irradiation for 1 h (red line). S 8

10 Figure S8. Co L-edge X-ray absorption spectra of Co(L-OMe)(OTf), Co(L-t-Bu)(OTf), and Co(L-Cl)(OTf), in comparison with Co III (L-t-Bu)(OAc). S 9

11 Figure S9. (a) Temperature dependence of the magnetic moment (µ eff ) of polycrystalline samples of Co II (L-t-Bu) (blue circle) and Co(L-t-Bu)(OTf) (red circle) in an applied field of 1 koe. The solid lines represent best fits with parameters for Co II (L-t-Bu): S = 1/2; g = 2.44; χ TIP = emu; θ = 1.4 K, and for Co III (L-t-Bu)(OTf): S = 1; [D] = 30 cm 1 ; E/D = 0.3; g = 2.08; χ TIP = emu. (b) Temperature dependence of the magnetic moment (µ eff ) of polycrystalline samples of Co II (L-Cl) (blue circle) and Co(L-Cl)(OTf) (red circle) in an applied field of 1 koe. The solid lines represent best fits with parameters for Co II (L-Cl): S = 1/2; g = 2.4; χ TIP = emu; θ = 1.5 K, and for Co III (L-Cl)(OTf): S = 1; [D] = 35 cm 1 ; E/D = 0.3; g = 2.11; χ TIP = emu. The simulation was done by julx written by E. Bill. Details for julx, see S 10

12 Figure S10. (a) Temperature dependence of the magnetic moment (µ eff ) of a polycrystalline sample of Co(L-OMe/t-Bu)(OTf) (red circle) in an applied field of 1 koe. The solid line represents the best fit with parameters for Co III (L-OMe/t-Bu)(OTf): S = 1; [D] = 36 cm 1 ; E/D = 0.3; g = 2.04; χ TIP = emu. (b) Temperature dependence of the magnetic moment (µ eff ) of a polycrystalline sample of Co(L-OMe/Cl)(OTf) (red circle) in an applied field of 1 koe. The solid line represents the best fit with parameters for Co III (L-OMe/Cl)(OTf): S = 1; [D] = 35 cm 1 ; E/D = 0.3; g = 2.12; χ TIP = emu. The simulation was done by julx written by E. Bill. Details for julx, see S 11

13 Figure S11. X-band EPR spectra of 2 mm frozen solution of (a) Co II (L-t-Bu) (blue line) and Co(L-t-Bu)(OTf) (red line), and (b) Co II (L-Cl) (blue line) and Co(L-Cl)(OTf) (red line). Conditions: temperature, 4K; solvent, frozen 30% toluene CH 2 Cl 2 ; microwave frequency, 9.65 GHz; microwave power, 0.5 mw; modulation amplitude, 7G; time constant, ms; conversion time, ms. S 12

14 Figure S12. Experimental (black line) and simulated (red line) EPR spectra of (a) Co II (L-OMe), (b) Co II (L-t-Bu), and (c) Co II (L-Cl). Experimental conditions are given in Figure 4 and Figure S11. The simulation was carried out using EasySpin with the simulation parameters as follows: (a) microwave frequency; GHz, g x = 2.75; g y = 2.00; g z = 1.90; A x = 180 G; A y = 36 G; A z = 4 G; line width (full width at half maximum), 150 G; temperature, 4.0 K. (b) microwave frequency; GHz, g x = 2.75; g y = 2.01; g z = 1.88; A x = 180 G; A y = 36 G; A z = 4 G; line width (full width at half maximum), 150 G; temperature, 4.0 K. (c) microwave frequency; GHz, g x = 2.75; g y = 2.02; g z = 1.87; A x = 250 G; A y = 36 G; A z = 4 G; line width (full width at half maximum), 200 G; temperature, 4.0 K. S 13

15 Chart S1. Selectively deuterated salen ligands for 2 H NMR measurements. In L-t-Bu-d 4, 2 H atoms are selectively incorporated into the phenolate rings (80% D) and the tert-butyl groups (7% D). The L-t-Bu-d 2 ligand is selectively deuterated at the 7/7 positions (99.5% D). S 14

16 Figure S13. 1 H NMR spectrum of 20 mm solution of Co II (L-t-Bu) in CD 2 Cl 2 at 298 K (black line). 2 H NMR spectra of 20 mm solution of Co II (L-t-Bu-d 4 ) (red line) and Co II (L-t-Bu-d 2 ) (blue line) in CH 2 Cl 2 at 298 K. The structures of selectively deuterated salen ligands, L-t-Bu-d 4 and L-t-Bu-d 2, are shown in Chart S1. The signals denoted with an asterisk come from residual CHDCl 2 and are referenced to 5.32 ppm. The signals denoted with t-bu and PhO arise from the tert-butyl and phenolate protons, respectively. The assignment of the tert-butyl groups was done by comparing the 1 H NMR spectra of Co II (L-OMe), Co II (L-t-Bu), and Co II (L-Cl) (Figure S15, Supporting Information). S 15

17 Figure S14. 1 H NMR spectrum of 20 mm solution of Co(L-t-Bu)(OTf) in CD 2 Cl 2 at 298 K (black line). 2 H NMR spectra of 20 mm solution of Co(L-t-Bu-d 4 )(OTf) (red line) and Co(L-t-Bu-d 2 )(OTf) (blue line) in CH 2 Cl 2 at 298 K. The structures of selectively deuterated salen ligands, L-t-Bu-d 4 and L-t-Bu-d 2, are shown in Chart S1. The signals denoted with an asterisk come from residual CHDCl 2 and are referenced to 5.32 ppm. The signals denoted with t-bu and PhO arise from the tert-butyl and phenolate protons, respectively. The assignment of the tert-butyl groups was done by comparing the 1 H NMR spectra of Co(L-OMe)(OTf), Co(L-t-Bu)(OTf), and Co(L-Cl)(OTf) (Figure S16, Supporting Information). S 16

18 Figure S15. at 298 K. 1 H NMR spectra of 20 mm solution of (a) Co II (L-OMe), (b) Co II (L-t-Bu), and (c) Co II (L-Cl) in CD 2 Cl 2 The signals designated with an asterisk come from residual CHDCl 2 and are referenced to 5.32 ppm. The signal at 1.5 ppm is assigned as arising from residual H 2 O. The signals designated with t-bu and PhO arise from the tert-butyl and phenolate protons in Co II (L-t-Bu), respectively, as determined by 2 H NMR spectra of Co II (L-t-Bu-d 4 ) (Figure S13, Supporting Information). The signal that arises from the azomethine proton in Co II (L-t-Bu) is determined by the 2 H NMR spectrum of Co II (L-t-Bu-d 2 ) (Figure S13, Supporting Information). S 17

19 Figure S16. 1 H NMR spectra of 20 mm solution of (a) Co(L-OMe)(OTf), (b) Co(L-t-Bu)(OTf), and (c) Co(L-Cl)(OTf) in CD 2 Cl 2 at 298 K. The signals designated with an asterisk come from residual CHDCl 2 and are referenced to 5.32 ppm. The signal at 3.4 ppm in (c) Co(L-Cl)(OTf) is assigned as arising from H 2 O. The signals designated with t-bu and PhO arise from the tert-butyl and phenolate protons in Co(L-t-Bu)(OTf), respectively, as determined by 2 H NMR spectra of Co(L-t-Bu-d 4 )(OTf) (Figure S14, Supporting Information). The signal arising from the MeO group is assigned by comparing the spectra of (a) (c). The signal that arises from the azomethine proton in Co(L-t-Bu)(OTf) is determined by the 2 H NMR spectrum of Co(L-t-Bu-d 2 )(OTf) (Figure S14, Supporting Information). S 18

20 Figure S17. 2 H NMR Curie plots and linear least-squares fits to the data for (a) Co II (L-t-Bu-d 4 ) and Co II (L-t-Bu-d 2 ). S 19

21 Figure S18. 1 H NMR Curie plots and linear least-squares fits to the data for (a) Co(L-OMe)(OTf), (b) Co(L-t-Bu)(OTf), (c) Co(L-t-Bu-d 2 )(OTf), (d) Co(L-OMe/t-Bu)(OTf), and (e) Co(L-OMe/Cl)(OTf). Temperature dependence of the 1 H NMR signals from Co(L-Cl)(OTf) cannot be determined due to signal broadening at lower temperatures. S 20

22 Figure S19. 1 H NMR spectrum of 20 mm solution of Co II (L-t-Bu) in pyridine-d 5 at 298 K (black line). 2 H NMR spectra of 20 mm solution of Co II (L-t-Bu-d 4 ) (red line) and Co II (L-t-Bu-d 2 ) (blue line) in pyridine at 298 K. Measurements were carried out under anaerobic Ar atmosphere. The structures of selectively deuterated salen ligands, L-t-Bu-d 4 and L-t-Bu-d 2, are shown in Chart S1. The signals denoted with an asterisk come from residual pyridine and are referenced to 8.71, 7.55, 7.19 ppm. The signals denoted with t-bu and PhO arise from the tert-butyl and phenolate protons, respectively. The assignment of the tert-butyl groups was done by comparing the 1 H NMR spectra of Co II (L-OMe), Co II (L-t-Bu), and Co II (L-Cl) in pyridine-d 6 (Figure S20, Supporting Information). The signal at 4.9 ppm is assigned as arising from residual H 2 O in pyridine-d 6. S 21

23 Figure S20. 1 H NMR spectra of 20 mm solution of (a) Co II (L-OMe), (b) Co II (L-t-Bu), and (c) Co II (L-Cl) in pyridine-d 5 at 298 K. Measurements were carried out under anaerobic Ar atmosphere. The signals designated with an asterisk come from residual pyridine and are referenced to 8.71, 7.55, 7.19 ppm. The signal at 4.9 ppm is assigned as arising from residual H 2 O. The signals designated with t-bu and PhO arise from the tert-butyl and phenolate protons in Co II (L-t-Bu), respectively, as determined by 2 H NMR spectra of Co II (L-t-Bu-d 4 ) in pyridine-d 5 (Figure S19, Supporting Information). S 22

24 Figure S21. 1 H NMR spectra of 20 mm solution of (a) Co II (L-OMe), (b) Co II (L-OMe/t-Bu), and (c) Co II (L-OMe/Cl) in CD 2 Cl 2 at 298 K. The signals designated with an asterisk come from residual CHDCl 2 and are referenced to 5.32 ppm. S 23

25 Figure S22. 1 H NMR spectra of 20 mm solution of (a) Co(L-t-Bu)(SbF 6 ), (b) Co(L-t-Bu)(OTf), and (c) Co(L-t-Bu)(OTs) in CH 2 Cl 2 at 298 K. The signals designated with an asterisk come from residual CHDCl 2 and are referenced to 5.32 ppm. The signals designated with t-bu and PhO arise from the tert-butyl and phenolate protons in Co(L-t-Bu)(OTf), respectively, as determined by 2 H NMR spectra of Co(L-t-Bu-d 4 )(OTf) (Figure S14, Supporting Information). The signal that arises from the azomethine proton in Co(L-t-Bu)(OTf) is determined by the 2 H NMR spectrum of Co(L-t-Bu-d 2 )(OTf) (Figure S14, Supporting Information). S 24

26 Figure S23. (a) Absorption spectra of Co II (L-OMe) (blue line), Co II (L-t-Bu) (red line), and Co II (L-Cl) (black line) in CH 2 Cl 2 at 298 K (0.5 mm, l = 0.1 cm). (b) Absorption spectra of Co II (L-OMe) (black line), Co II (L-OMe/t-Bu) (blue line), and Co II (L-OMe/Cl) (red line) in CH 2 Cl 2 at 298 K (0.5 mm, l = 0.1 cm). No absorption is observed in the range > 700 nm. S 25

27 Figure S24. Absorption spectra of (a) Co(L-OMe)(OTf), (b) Co(L-t-Bu)(OTf), and (c) Co(L-Cl)(OTf) in the solid state (red line) and in CH 2 Cl 2 at 298 K (0.5 mm, l = 0.1 cm, black line). The absorption spectra in the solid are shown using absorbance (right axis), and the absorption spectra in CH 2 Cl 2 are shown using ε (left axis). S 26

28 Figure S25. Absorption spectra of Co(L-OMe)(OTf) in CH 2 Cl 2 at 298, 253 and 213 K (0.5 mm, l = 0.1 cm). S 27

29 Figure S26. ESI-MS spectra in CH 3 OH at the cone voltage of 40 V (top) and theoretical isotope distribution patterns for [Co(salen)] + (bottom) of (a) Co(L-OMe/t-Bu)(OTf) and (b) Co(L-OMe/Cl)(OTf). The ion signals that arise from symmetrical cobalt salen complexes, m/z , in (a) and m/z , in (b) are not detected at all. S 28

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