Electronic, Magnetic, Redox Properties and O 2 Reactivity of Fe(II) Uncovering the Intradiol Cleaving Reactivity of an Fe(II)-osemiquinonate

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1 Electronic Supporting Information Electronic, Magnetic, Redox Properties and O 2 Reactivity of Fe(II) and Ni(II)-o-Semiquinonate Complexes of a Tris(thioether) Ligand: Uncovering the Intradiol Cleaving Reactivity of an Fe(II)-osemiquinonate complex Peng Wang, Michelle M. Killian, Mohamed R. Saber, Tian Qiu, Glenn P. A. Yap, Codrina V. Popescu, ǁ Joel Rosenthal, Kim R. Dunbar, Thomas C. Brunold, and Charles G. Riordan*, Department of Chemistry & Biochemistry, University of Delaware, Newark, Delaware 19716, United States Department of Chemistry, University of Wisconsin-Madison, Madison, Wisconsin 53706, United States Department of Chemistry, Texas A&M University, College Station, Texas , United States ǁ Department of Chemistry, Colgate University, 13 Oak Drive, Hamilton, New York 13346, United States riordan@udel.edu

2 Table S1. Crystallographic data for [PhTt tbu ]NiI, [PhTt tbu ]Ni(phenSQ) and [PhTt tbu ]Ni(3,5- DBSQ). Compound [PhTt tbu ]NiI [PhTt tbu ]Ni(phenSQ) [PhTt tbu ]Ni(3,5-DBSQ) Code Char391 Char425 Char343 Empirical C 21 H 38 BINiS 3 C 35 H 46 BNiO 2 S 3 C 35 H 58 BNiO 2 S 3 Formula Formula Weight Temperature, K 200(2) 200(2) 200(2) Wavelength, Å Crystal System Orthorhombic Monoclinic Monoclinic Space Group Pbca P2 1 /n C2/c a, Å (6) (9) (13) b, Å (9) (15) (5) c, Å (2) (19) (9) α, deg β, deg (17) (10) γ, deg V, Å (5) (5) (5) Z Density, Mg/m F(000) Crystal Size, mm x x x x x x θ Range, deg to to to R(F), Rw(F) , , ,

3 Figure S1. Molecular structure of [PhTt tbu ]NiI with atom labeling. Thermal ellipsoids are drawn to 30% probability. Hydrogen atoms have been omitted for clarity. Table S2. Selected bond lengths (Å) and bond angles ( ) for [PhTt tbu ]NiI. Length (Å) Angle ( ) Ni1 S (6) S1 Ni1 S (2) Ni1 S (6) S1 Ni1 S (2) Ni1 S (6) S2 Ni1 S (2) Ni1 I (5) S1 Ni1 I (5) Figure S2. 1 H NMR spectrum of [PhTt tbu ]NiI recorded in *C 6 D 6.

4 Figure S3. 1 H NMR spectrum of [PhTt tbu ]Ni(phenSQ) recorded in *C 6 D 6. The peak marked with the triangle ( ) is due to CH 2 Cl 2 in the atmosphere of the glovebox. The peak marked with the black dot ( ) is due to the residual pentane. The peaks marked with the black diamond ( ) arise from silica grease and TMS. Figure S4. 1 H NMR spectrum of [PhTt tbu ]Ni(3,5-DBSQ) recorded in *C 6 D 6. The peak marked with the triangle ( ) is due to CH 2 Cl 2 in the atmosphere of the glovebox. The peak marked with the black dot ( ) is due to the residue pentane. The peaks marked with the black diamond ( ) arise from silica grease and TMS.

5 calculated experimental Figure S5. Calculated (top) and experimental (bottom) high resolution LIFDI mass spectra of [PhTt tbu ]Ni(phenSQ).

6 experimental calculated Figure S6. Calculated (top) and experimental (bottom) high resolution LIFDI mass spectra of [PhTt tbu ]Ni(3,5-DBSQ).

7 Magnetization (B.M.) Magnetic field (Oe) Figure S7. Saturation magnetization data for [PhTt tbu ]Fe(phenSQ) at 1.8 K. Magnetization (B.M.) T 2 T 3 T 4 T 5 T 6 T 7 T Theory H/T (koe/k) Figure S8. Reduced magnetization data for [PhTt tbu ]Fe(phenSQ) at K. The red lines represent the best fits produced by PHI program using the D parameter.

8 1 Magnetization (B.M.) Magnetic field (Oe) Figure S9. Field dependent magnetization data for [PhTt tbu ]Ni(3,5-DBSQ) at 1.8 K. The red circles and red line represent the experimental data. The black line represents an S = 1/2 system without intermolecular interactions. 1 Magnetization (B.M.) Magnetic field (Oe) Figure S10. Field dependent magnetization data for [PhTt tbu ]Ni(phenSQ) at 1.8 K. The red circles and red line represent the experimental data. The black line represents an S = 1/2 system without intermolecular interaction.

9 Figure S11. Comparison of the experimental electronic spectrum of [PhTt tbu ]Fe(phenSQ) and the TD-DFT calculated spectrum for model Fe(phenSQ)2.

10 Figure S12. Comparison of the experimental electronic spectrum of [PhTt tbu ]Ni(phenSQ) and the TD-DFT calculated spectrum for model Ni(phenSQ)2..

11 Figure S13. Comparison of the experimental electronic spectrum of [PhTt tbu ]Ni(3,5-DBSQ) and the TD-DFT calculated spectrum for model Ni(3,5-DBSQ)2..

12 Figure S14. Comparison of the experimental electronic spectrum of [PhTt tbu ]Ni(3,5-DBSQ) and the TD-DFT calculated spectrum for model Ni(3,5-DBSQ)3. EDDMs for the relevant transitions are shown on top of the computed spectrum.

13 Figure S15. Qualitative MO diagram for model Ni(3,5-DBSQ)3 derived from the DFT results.

14 Figure S16. EDDMs for select TD-DFT calculated electronic transitions for model Fe(phenSQ)3. Regions with a gain and a loss in electron density are depicted in blue and white, respectively.

15 Figure S17. EDDMs for select TD-DFT calculated electronic transitions for model Ni(phenSQ)3. Regions with a gain and a loss in electron density are depicted in blue and white, respectively.

16 Figure S18. EDDMs for select TD-DFT calculated electronic transitions for model Ni(3,5- DBSQ)3. Regions with a gain and a loss in electron density are depicted in blue and white, respectively.

17 1.2 Abs Ni(3,5-DBSQ) + dioxygen at t = 0 t = 12 h Wavelength (nm) Figure S19. Electronic absorption spectra of [PhTt tbu ]Ni(3,5-DBSQ) under an O 2 atmosphere at t = 0 (solid green line) and at t = 12 h (dashed black line).

18 Figure S20. GC of phenthrenequinone (ca. 1mg/mL) with the same concentration of dodecane as the internal standard.

19 Figure S21. GC of diphenic anhydride (ca. 1mg/mL) with the same concentration of dodecane as the internal standard.

20 Figure S22. GC of the organic products of the reaction of [PhTt tbu ]Fe(phenSQ) (30 mg, mmol) with O 2. Dodecane (7.69 mg, mmol) was added as the internal standard and the solution was diluted to a concentration of ca mg dodecane/ml.

21 Figure S23. GC of the organic products of the reaction of [PhTt tbu ]Ni(phenSQ) (30 mg, mmol) with O 2. Dodecane (7.69 mg, mmol) was added as the internal standard and the solution was diluted to a concentration of ca mg dodecane/ml.

22 Figure S24. Calculated mass spectrum of 2-phenylphenanthro[9,10-d][1,3,2]dioxaborole (top); Calculated mass spectrum of 2-phenoxyphenanthro[9,10-d][1,3,2]dioxaborole (middle); Experimental LIFDI mass spectrum (m/z = 280 to 340 region) of the products of [PhTt tbu ]Fe(phenSQ) + O 2 (bottom).

23 Fe(phenSQ) 100 mv/s Fe(phenSQ) 200 mv/s Fe(phenSQ) 300 mv/s Fe(phenSQ) 500 mv/s Fe(phenSQ) 1000 mv/s 10 μa E vs. Fc +/0 (V) Figure S25. Cyclic voltammograms (cathodic sweeps) of [PhTt tbu ]Fe(phenSQ) in THF (1.0 mm) containing 0.1 M n-bu 4 NClO 4 at various scan rates (100 mv/s (brown); 200 mv/s (red); 300 mv/s (green); 500 mv/s (purple); 1000 mv/s (blue)).