Electronic Supplementary Material (ESI) for Dalton Transactions. This journal is © The Royal Society of Chemistry 2018 Supporting Information Catalytic and stoichiometric flavanone oxidations mediated by nonheme oxoiron(IV) complexes as flavone synthase mimics: kinetic, mechanistic and computational studies Ramona Turcas,a Balázs Kripli,a Amr A. A. Attia,b Dóra Lakk-Bogáth,a Gábor Speier,a Michel Giorgi,c Radu Silaghi-Dumitrescu,*b and József Kaizer*a aDepartment of Chemistry, University of Pannonia, H-8201 Veszprém, Hungary E-mail: kaizer@almos.vein.hu. Department of Chemistry, Babes-Bolyai University, 1, Kogalniceanu Str., 400084 ClujNapoca, Romania c Aix Marseille Université, CNRS, Centrale Marseille, Spectropole FR1739, 13397 Marseille, France b List of Contents Materials ..................................................................................................................................2 Instrumentation ........................................................................................................................2 Synthesis and characterization .................................................................................................2 Oxidation reactions ..................................................................................................................9 Description of the Fe(IV) intermediate formations with PhIO and their stoichiometric oxidation with flavanone.......................................................................................................13 Theoretical methods...............................................................................................................19 References..............................................................................................................................21 Cartesian coordinates for all optimized structures including absolute energies and imaginary frequencies for transition states. ...............................................................................................22 1 Materials All syntheses were done under an argon atmosphere unless stated otherwise. Solvents used for the synthesis and reactions were purified by standard methods and stored under argon. The starting materials for the ligand are commercially available and they were purchased from Sigma-Aldrich. Instrumentation The crystal evaluation and intensity data collection for 3 was performed on a Bruker-Nonius Kappa CCD single-crystal diffractometer using Mo K radiation ( = 0.71073 Å) at 293 K. Crystallographic data and selected bond lengths and angles are listed in Table S1, Table S2, and Table S3 whereas details of the structure determination are given in Figure S2. Comparison with similar N4Py-based complexes has been made and data is shown in Table S3. SHELX–2013 [1] was used for structure solution and full matrix least squares refinement on F2. The UV-visible spectra were recorded on an Agilent 8453 diode-array spectrophotometer using quartz cells. IR spectra were recorded using a Thermo Nicolet Avatar 330 FT-IR instrument (Thermo Nicolet Corporation, Madison, WI, USA). Samples were prepared in the form of KBr pellets. GC analyses were performed on an Agilent 6850 gas chromatograph equipped with a flame ionization detector and a 30 m SUPELCO BETA DEX225 column. ESI- MS samples were analyzed using triple quadruple Micromass Quattro spectrometer (Waters, Milford, MA, USA), that was operated in positive electrospray ionization mode. NMR spectrum was recorded on a Bruker Avance 400 spectrometer (Bruker Biospin AG, Fällanden, Switzerland). Microanalyses (elemental analysis) were done by the Microanalytical Service of the University of Pannonia. Synthesis and characterization Preparation of the N4Pys [2,3]. The amine from the previous experiment was used without any purification. It was mixed with 2.2 eq. 2-(chloromethyl)pyridine (or quinoline) hydrochloride (26 mmol) and 20 eq. K2CO3 (240 mmol) in 200 ml MeCN and 10 ml water. The mixture was refluxed for 20 hours then (after cooling down) filtered from excess 2 carbonate. The clear red solution was evaporated partially under reduced pressure. 15 ml water was added and the crude product was extracted with dichloromethane. The organic layer was dried with NaSO4 then solvent was evaporated. The crude brown oil was dissolved in acetone and filtered to result the product as white powder (27-54%). Scheme S1. Synthesis of asymmetric N4Pys (asN4Py and asN2Py2Q). Compound Characterization. 1,2-di(2-pyridyl)ethanone oxime: colorless crystal, 25%; 1HNMR (400 MHz, CDCl3): 10.22 (s, 1 H), 8.61-8.45 (m, 2 H), 7.97 (d, J = 8, 1 H), 7.67-7.52 (m, 2 H), 7.33 (d, J = 8, 1 H), 7.24-7.17 (m, 1 H), 7.13-7.06 (m, 1 H), 4.62 (s, 2 H). Anal. Calcd. for C12H11N3O: C, 67.59; H, 5.20; N, 19.71. Found C, 67.41; H, 5.22; N, 19.66. 1-(2-quinolyl)-2-(2-pyridyl)ethanone oxime: beige crystal, 20%; 1H-NMR (400 MHz, DMSO): 11.86 (s, 1 H), 8.37 – 8.32 (m, 2 H), 8.10 (d, J = 9 Hz, 1 H), 7.99 – 7.91 (m, 2 H), 7.76 – 7.70 (m, 1 H), 7.66 – 7.56 (m, 2 H), 7.23 (dt, J = 8 Hz, 1 Hz, 1 H), 7.15 – 7.10 (m, 1 H), 4.56 (s, 2 H). Anal. Calcd. for C16H13N3O: C, 72.99; H, 4.98; N, 15.96. Found C, 72.90; H, 4.99; N, 15.89. N,N-bis(2-pyridylmethyl)-1,2-di(2-pyridyl)ethylamine (asN4Py): white solid, 27%; 1H-NMR (400 MHz, DMSO): 8.60-8.56 (m, 1 H), 8.42-8.39 (m, 2 H), 8.38-8.35 (m, 1 H), 7.74 (dt, J = 8, 2, 1 H), 7.63-7.53 (m, 3 H), 7.34-7.29 (m, 1 H), 7.28-7.09 (m, 7 H), 4.46 (t, J = 7, 1 H), 4.03 (d, J = 15, 2 H), 3.64 (d, J = 15, 2 H), 3.53 (dd, J = 14, 7, 1 H), 3.45 (dd, J = 14, 7, 1 H). Anal. Calcd. for C24H23N5: C, 75.56; H, 6.08; N, 18.36. Found C, 75.47; H, 6.10; N, 18.32. 3 N,N-bis(2-quinolylmethyl)-1,2-di(2-pyridyl)ethylamine (asN2Py2Q): light brown solid, 54%; 1H-NMR (400 MHz, CDCl3): 8.67 (d, J = 4, 1 H), 8.43 (d, J = 4, 1 H), 8.14-7.95 (m, 4 H), 7.78-7.63 (m, 6 H), 7.49 (q, J = 7, 3 H), 7.33 (d, J = 9, 3 H), 7.23-7.09 (m, 2 H), 4.49 (t, J = 7, 1 H), 4.34 (d, J = 15, 2 H), 3.86 (d, J = 15, 2 H), 3.81 (dd, J = 14, 7, 1 H), 3.50 (dd, J = 14, 7, 1 H). Anal. Calcd. for C32H27N5: C, 79.81; H, 5.65; N, 14.54. Found C, 79.65; H, 5.66; N, 14.48. Figure S1. 1H-NMR spectrum of asN2Py2Q in DMSO. Preparation of [FeII(asN2Py2Q)(Cl)](ClO4) (3): 0.407 g (0.786 mmol) ligand, asN2Py2Q.HCl and 0.285 g (0.786 mmol) FeII(ClO4)2 × 6H2O were dissolved in 4 ml MeOHMeCN (1:1) mixture under Ar. The mixture was stirred at RT for 3 hour. 1.5 ml EtOAc was layered onto the surface of the solution and it was placed to the freezer (-40°C). Cubic shaped red crystals formed during overnight. Yield: 0.42 g (80%). FT-IR (KBr, cm−1): 3441 m, 3066 w, 1622 w, 1603 m, 1513 m, 1433 m, 1377 w, 1296 w, 1091 s, 826 m, 784 m, 756 m, 625 m. UV–Vis (MeCN) max(log ε, dm3mol−1cm−1): 300 (4.04), 380 (3.00), 440 (2.77). Anal. Calcd. for C32H27Cl2FeN5O4 (672.34): C, 57.16; H, 4.05; N, 10.42. Found C, 57.23; H, 4.11; N, 10.37. 4 [FeII(asN2Py2Q)(CH3CN)](ClO4)2 (3a): It was prepared by reacting FeII(ClO4)2 × 6H2O with asN2Py2Q ligand (The free ligand was obtained from asN2Py2Q.HCl and NEt3, extracted with CH2Cl2.) in acetonitrile. E1/2 = 0.83 V vs. SCE. Anal. Calcd. for C34H30Cl2FeN6O8: C, 52.53; H, 3.89; N, 10.81. Found C, 52.67; H, 3.76; N, 10.74. Table S1. Summary of crystal data and intensity collection and structure refinement parameters for [FeII(asN2Py2Q)Cl]ClO4 Compound [FeII(asN2Py2Q)Cl]ClO4 Chemical formula C39H40.5Cl2FeN5O7.5 Formula weight 826.01 Crystal system triclinic Space group P-1 a (Å) 12.3536(3) b (Å) 12.7733(4) c (Å) 15.3745(3)   75.982(2) (°) 61.907(3)  (°) Volume (Å3) 1983.54(12) Z 2 Calc. density (g cm-1) 1.383 Temperature (K) 173 Abs. coeff. (mm-1) 4.755 F (0 0 0) 859 Obs. reflections 7432 Goodness-of-fit 1.063 R1a 0.0556 wR2 0.1593 a w=1⁄[σ2(F 2)+(αP)2+bP] and P = (max F 2,0)+2F 2)/3 o o c R1 = Σ(|Fo|-|Fc|)/Σ(|Fo|) and wR2 = {Σ[w(Fo2-Fc2)2]/Σ[w(Fo2)2]}1/2. Table S2. Selected bond distances (Å) and angles (°) for [FeII(asN2Py2Q)Cl]ClO4 complex distances Fe(1) – Cl(1) Fe(1) – N(2) Fe(1) – N(3) Fe(1) – N(4) Fe(1) – N(5) Fe(1) – N(1) 2.321(1) 2.254(2) 2.230(2) 2.292(2) 2.220(3) 2.203(3) angles N(1)-Fe(1)-N(2) 90.0(1) N(1)-Fe(1)-N(4) 75.34(9) N(2)-Fe(1)-N(3) 80.63(9) N(4)-Fe(1)-N(5) 84.38(9) N(2)-Fe(1)-N(5) 81.07(9) N(1)-Fe(1)-Cl(1) 160.77(7) 5 Table S3. Comparison of different Fe−N bond distances (Å) between Fe(N4Py) derivates (Ndiv = diverse or nonregular pyridyl moiety) entry [FeII(asN4Py)(MeCN)](ClO4)2 [FeII(N3PyBzIM)(MeCN)](ClO4)2 [FeII(N2Py2BzIM)(MeCN)](ClO4)2 [FeII(N4Py)(MeCN)](ClO4)2 [FeII(asN2Py2Q)Cl](ClO4) Fe–Npy (av) 1.968 1.953 1.974 1.972 2.242 Fe–Ndiv (av) 2.037(3) 1.977 1.981 2.256 Fe–NMeCN Fe–Namine ref. 1.944(4) 1.909(6) 1.901(3) 1.915(3) - 1.972(4) 1.980(6) 2.028(2) 1.961(3) 2.203(3) [4] [5] [5] [6] [this work] Figure S2. X-ray structure of 3. Thermal ellipsoids are plotted at 50% probability level. Outer sphere solvent molecules, hydrogen atoms were omitted for clarity. (CCDC 1841256). 6 11-Apr-2016 1604011-VP-BOB32TISZTA-POZ1 45 (1.169) Cm (45:49) 268.8 % 100 Scan ES+ 1.28e8 572.1 284.1 248.3 0 250 574.1 289.2 324.1 353.1 300 350 636.2 400 450 500 550 600 650 700 750 800 Figure S3. Electrospray ionization mass spectrum of [FeII(asN2Py2Q)Cl]ClO4 complex. The peaks at m/z = 268.8 and m/z = 289.2 correspond to the formulations [FeII(asN2Py2Q)]2+ (calcd 268.6) and [FeII(asN2Py2Q)(CH3CN)]2+ (calcd 289.6), respectively, as well as peaks at m/z = 572.1 and m/z = 636.2 correspond to the formulations [FeII(asN2Py2Q)(Cl)]+ (calcd 572.1) and [FeII(asN2Py2Q)(ClO4)]+ (calcd 636.1), respectively. Figure S4. UV−Vis spectra of complexes [FeII(asN2Py2Q)(Cl)](ClO4) (blue), [FeII(asN4Py)(MeCN)](ClO4)2 (red) (0.20 mM) and [FeII(N4Py)(MeCN)](ClO4)2 (green) in acetonitrile recorded at room temperature (298 K). 7 m/z Figure S5. Cyclic voltammograms of 1 mM [FeII(N4Py)(MeCN)](ClO4)2 (green), [FeII(asN4Py)(MeCN)](ClO4)2 (red) and [FeII(asN2Py2Q)(Cl)](ClO4) (blue) in CH3CN with 0.1 M (Bu4N)ClO4; scan rate 100 mVs-1; working electrode: glassy carbon electrode (GCE), auxiliary electrode: Pt wire, reference electrode: Ag/AgCl. 11-Apr-2016 1604011-VP-FEASN4PYCLO4OLDFE4-POZ1 9 (0.234) Cm (9:16) Scan ES+ 1.13e8 276.6 100 % 284.1 268.4 341.2 0 200 300 353.1 393.1 400 482.3 500 652.1 667.2 600 700 800 900 1000 m/z 1100 Figure S6. Electrospray ionization mass spectrum of 6. The peaks at m/z = 276.6 (z = 2) and 652.1 (z = 1)correspond to the formulae [FeIV(O)(asN2Py2Q)]2+ (m/z calcd 276.6) and [FeIV(O)(asN2PyQ2)(ClO4)]+ (m/z calcd 652.1), respectively. 8 Oxidation reactions Reaction conditions for catalysis In a typical reaction, 2 ml of 337.5 mM mCPBA solution in CH3CN was delivered by syringe pump in air or under argon to a stirred 1 ml solution of catalyst (9 mol), and the substrate (3 mmol) inside a vial. The final concentrations of the reagents were 3 mM iron catalyst, 225 mM mCPBA, and 1000 mM flavanone. After syringe pump addition (5 min the solution was stirred for 5 minutes and a known amount of PhBr (0.315 mmol) was added as an internal standard. The iron complex was removed by passing the reaction mixture through a silica column followed by elution with ethyl acetate. The products (1,3-dione (D) and flavone) were identified by GC/MS and confirmed by comparison with authentic samples. Flavone is commercially available and it was purchased from Sigma-Aldrich. 1-(2-hydroxy-phenyl)-3phenyl-propane-1,3-dione (D): o-Benzoyloxyacetophenone has been prepared by the action of benzoyl chloride on a pyridine solution of o-hydroxyacetophenone. Its rearrangement to 1-(2hydroxy-phenyl)-3-phenyl-propane-1,3-dione (D) by alkali has been described [7]. Yield: 80– 85%; m.p. 117–120 °C. GC-MS spectrum: m/z: 240 (13.7 %), 121 (23.1 %), 105 (100 %), 77 (63.3 %), 69 (13.1 %), 65 (24.7 %), 51 (26.4 %), 39 (23.4 %). Figure S7. GC-MS spectrum of 2-hydroxy-flavanone (A): m/z: 240 (16.9 %), 224 (72,6 %), 163 (11 %), 136 (20.5 %), 120 (100 %), 105 (15,4 %). 9 Figure S8. GC-MS spectrum of 1-(2-hydroxy-phenyl)-3-phenyl-propane-1,3-dione (D): m/z: 240 (16,1 %), 223 (6,3 %), 121 (22,4 %), 120 (5,3 %), 106 (7,2 %), 105 (100 %), 77 (33 %), 69 (8.0 %), 65 (11,4 %), 51 (6,5 %), 39 (7,5 %). Figure S9. GC-MS spectrum of flavone (F): m/z: 223 (72 %), 222 (100 %), 194 (46,4 %), 120 (83,4 %), 92 (59,6 %). 10 Table S4. Catalytic flavanone oxidation in acetonitrile at 25°C by mCPBA using compound 1, 2 and 3. Entry Conditions Product Yielda TON (%) 1 [Fe(ClO4)2] : [mCPBA] : [FlaH2] Flavone 1.6 1.2 3 : 225 :1000 A D 2 [1] : [mCPBA] : [FlaH2] Flavone 11.8 2.95 3 : 75 :1000 A 0.05 0.01 D 0.59 0.15 3 [1] : [mCPBA] : [FlaH2] Flavone 14.6 10.9 3 : 225 :1000 A 0.13 0.10 D 1.4 1.05 4 [1] : [mCPBA] : [FlaH2] Flavone 14.4 21.6 3 : 450 :1000 A 0.07 0.11 D 0.44 0.66 5 [2] : [mCPBA] : [FlaH2] Flavone 10.7 2.85 3 : 75 :1000 A D 0.68 0.17 6 [2] : [mCPBA] : [FlaH2] Flavone 9.25 6.93 3 : 225 :1000 A 0.03 0.02 D 0.14 0.11 7 [3] : [mCPBA] : [FlaH2] Flavone 22.0 5.5 3 : 75 :1000 A 0.02 0.01 D 0.23 0.06 8 [3] : [mCPBA] : [FlaH2] Flavone 17.9 13.4 3 : 225 :1000 A 0.03 0.03 D 0.59 0.74 9 [3a] : [mCPBA] : [FlaH2] Flavone 25.5 19.5 3 : 225 :1000 A 0.02 0.02 D 0.54 0.4 10b [3a] : [mCPBA] : [FlaH2] Flavone 16.5 12.4 3 : 225 :1000 A 0.04 0.03 D 11.1 8.31 11 [3] : [mCPBA] : [FlaH2] Flavone 5.76 13.0 1 : 225 :1000 A D 0.1 0.23 12 [3] : [mCPBA] : [FlaH2] Flavone 25.7 11.7 5 : 225 :1000 A D 0.21 0.10 aBased on oxidant. bIn the presence of H 18O (37 mM) and H 16O (47 mM) coming from the 2 2 oxidant, mCPBA. 11 % 77 92 75 51 50 105 120 65 39 147 25 121 136 0 25.0 50.0 75.0 100.0 125.0 163 181 195 150.0 175.0 200.0 240 242 224 225.0 Figure S10. Catalytic flavanone oxidation in acetonitrile at 25°C by mCPBA using compound 3a (Table S4, Entry 10). GC-MS spectrum of 2-hydroxy-flavanone (A) in the presence of H218O (37 mM) (and H216O (47 mM) coming from the oxidant, mCPBA) m/z: 242 (8.38 %), 240 (11.67 %), 224 (12.94 %), 163 (7.56 %), 136 (19.17 %), 120 (50.80 %), 105 (46.98 %), 77 (100 %). % 100 105 77 75 51 39 50 65 92 25 121 136 38 181 0 25.0 50.0 75.0 100.0 125.0 150.0 175.0 207 200.0 223 240 225.0 250.0 12 Figure S11. Catalytic flavanone oxidation in acetonitrile at 25°C by mCPBA using compound 3a (Table S4, Entry 10). GC-MS spectrum of 1-(2-hydroxy-phenyl)-3-phenylpropane-1,3-dione (D) in the presence of H218O (37 mM) (and H216O (47 mM) coming from the oxidant, mCPBA) m/z: 242 (5.75 %), 240 (13.34 %), 223 (11.86 %), 121 (37.81 %), 120 (14.25 %), 106 (10.47 %), 105 (100 %), 77 (92.18 %), 69 (7.43 %), 65 (35.49 %), 51 (62.43 %), 39 (45.33 %). Description of the Fe(IV) intermediate formations with PhIO and their stoichiometric oxidation with flavanone 1, 2 or 3 complex (1.5 × 10-3 M) was dissolved in acetonitrile (1.5 mL), then iodosylbenzene (2.00 × 10-3 M) was added to the solution. The mixture was stirred for 50, 50 or 4 minutes, respectively, then the excess iodosylbenzene was removed by filtration. Flavanone (0.6 M) was added to the solution and the reaction was monitored by UV-vis spectrophotometer (Agilent 8453) at 695, 705 or 805 nm ( = 400, 400, 280 M-1 cm-1). 18O-labeled experiments in the presence of H218O (18 mM) were also carried out: Flavone (F, yields 70-80%, based on the intermediates generated) m/z: 223 (7.54 %), 222 (49.27 %), 194 (36.41 %), 120 (57.76 %), 105 (100 %), 92 (100 %). GC-MS spectrum of 1-(2-hydroxy-phenyl)-3-phenyl-propane-1,3-dione (D, yields 5-10% based on the intermediates generated) m/z: 242 (2.44 %), 223 (22.79 %), 121 (15.62 %), 120 (62.09 %), 106 (1.43 %), 105 (6.47 %), 77 (53.41 %). 13 Table S5. The calculated v, kobs and k2 values in the reaction of 4 and flavanone in MeCN. N0 T [4]0 Flavanon kobs k2 1 2 3 4 5 6 7 8 9 (K) 298 298 298 298 298 288 293 303 308 (10-3 M) 1.5 1.5 1.5 1.5 1.5 1.5 1.5 1.5 1.5 (M) 0.3 0.45 0.6 0.75 0.9 0.75 0.75 0.75 0.75 (10-4s-1) 1.70 2.49 3.30 4.29 5.05 2.59 3.26 4.98 6.35 (10-3 M-1s-1) 0.57±0.03 0.55±0.03 0.55±0.03 0.57±0.04 0.56±0.03 0.35±0.01 0.44±0.01 0.66±0.02 0.85±0.04 Table S6. The calculated v, kobs and k2 values in the reaction of 5 and flavanone in MeCN. N0 T [Fe]0 Flavanon kobs k2 1 2 3 4 6 7 8 9 10 (K) 298 298 298 298 288 293 303 308 313 (10-3 M) 1.5 1.5 1.5 1.5 1.5 1.5 1.5 1.5 1.5 (M) 0.3 0.6 0.75 0.9 0.75 0.75 0.75 0.75 0.75 (10-4s-1) 0.65 1.35 1.83 2.28 0.43 0.74 2.11 3.39 4.55 (10-3 M-1s-1) 0.22±0.01 0.23±0.01 0.24±0.01 0.25±0.01 0.06±0.003 0.10±0.006 0.28±0.01 0.45±0.02 0.61±0.03 Table S7. The calculated v, kobs and k2 values in the reaction of 6 and flavanone in MeCN. N0 T [Fe]0 Flavanon kobs k2 1 2 3 4 6 7 8 9 10 (K) 298 298 298 298 298 278 283 288 293 (10-3 M) 1.5 1.5 1.5 1.5 1.5 1.5 1.5 1.5 1.5 (M) 0.15 0.3 0.45 0.6 0.75 0.75 0.75 0.75 0.75 (10-3s-1) 3.19 5.96 7.68 11.1 14.2 3.27 4.90 7.38 9.58 (10-3 M-1s-1) 21.27±1.3 19.87±0.79 17.07±0.68 18.42±0.92 19.20±1.1 4.36±0.17 6.50±0.32 9.84±0.39 12.77±0.63 14 Figure S12. UV-vis spectral change of 6 (1.5 mM) upon addition of flavanone (0.6 M) at 298 K. Inset shows time course of the decay of 6 monitored at 705 nm. Figure S13. UV-vis spectral change of 6 (1.5 mM) upon addition of flavanone (0.6 M) at 298 K. Inset shows time course of the decay of 6 monitored at 805 nm 15 Figure S14. Reaction rates versus flavanone concentration in MeCN at 25 °C. [4]0 = 1.50 × 10-3 M. Figure S15. Reaction rates versus flavanone concentration in MeCN at 25 °C. [5]0 = 1.50 × 10-3 M. 16 Figure S16. Reaction rates versus flavanone concentration in MeCN at 25 °C. [6]0 = 1.50 × 10-3 M. Figure S17. Arrhenius plot of the reaction of 4 and flavanone in MeCN. [4]0 = 1.50 × 10-3 M, [flavanone]0 = 0.75 M. 17 Figure S18. Arrhenius plot of the reaction of 5 and flavanone in MeCN. [5]0 = 1.50 × 10-3 M, [flavanone]0 = 0.75 M. Figure S19. Arrhenius plot of the reaction of 6 and flavanone in MeCN. [6]0 = 1.50 × 10-3 M, [flavanone]0 = 0.75 M. 18 Theoretical methods Geometry optimizations were carried out on the [N4PyFe4+O]2+ + flavanone model complex without any constraints at the M06L/6-31g(d,p) level of theory [8] as implemented in the Gaussian09 software package [9]. The optimized ([N4PyFe4+O]2+ + flavanone) model complex is depicted in figure 1. Initial calculations on the [N4PyFe4+O]2+ model structure led to an intermediate (S=1) ground state and thus, only the S=1 spin state was utilized in all further calculations. All transition states were characterized by one imaginary frequency and confirmed using IRC calculations. Single point energy calculations were then performed on the optimized structures by utilizing the same DFT functional and the def2-TZVP basis set. Calculations were performed in water using the CPCM solvation model [10] and accounting for Grimme’s empirical dispersion correction [11]. Thus, the final free energies are those obtained with the higher basis set including zero-point corrections, thermal corrections and entropy at (298.15K), as well as solvent and dispersion corrections. Figure S20. The optimized structure of the [N4PyFe4+O]2+ + flavanone model complex 19 Figure S21. M06-L/def2-TZVP DFT results for the proposed reaction mechanism (1) involving the formation of 3-hydroxy-flavanone through H-atom abstraction from flavanone’s C3 by [N4PyFe4+O]2+ to form the enzyme-like product flavone. Figure S22. M06-L/def2-TZVP DFT results for the proposed reaction mechanism (2) involving a direct 2 H-atom abstraction step by [N4PyFe4+O]2+ leading to the formation of the enzyme-like product flavone without a hydroxy-flavanone intermediate. 20 References [1] G. M. Sheldrick, Acta Crystallogr. 2008, A64, 112. [2] M. Lubben, A. Meetsma, E. C. Wilkinson, B. Feringa, L. Que Jr. Angew. Chem. Int. Ed. Engl. 1995, 34, 1512. [3] S. Negi, M. Matsukura, M. Mizuno, K. Miyake, N. Minami, Synthesis 1996, 991. [4] D. Lakk-Bogáth, R. Csonka, G. Speier, M. Réglier, A. J. Simaan, J. V. Naubron, M. Giorgi, K. Lazar, J. Kaizer, Inorg. Chem., 2016, 55, 10090; [5] M. Mitra, H. Nimir, S. Demeshko, S. S. Bhat, S. O. Malinkin, M. Haukka, J. Lloret-Fillol, G. C. Lisensky, F. Meyer, A. A. Shteinman, W. R. Browne, D. A. Hrovat, M. G. Richmond, M. Costas, E. Nordlander, Inorg. Chem. 2015, 54, 7152. [6] G. Roelfes, M. Lubben, K. Chen, R. Y. N. Ho, A. Meetsma, S. Genseberger, R. M. Hermant, R. Hage, S. K. Mandal, V. G. Young Jr., Y. Zang, H. Kooijman, A. L. Spek, L. Que Jr., B. L. Feringa, Inorg. Chem. 1999, 38, 1929. [7] T. S. Wheeler, Org. Synth. 1952, 32, 72. [8] Y. Zhao, D. Truhlar, Theor Chem Account. 2008, 120, 215-241 [9] Gaussian 09, Revision E.01, M.J. Frisch, G.W. Trucks, H.B. Schlegel, G.E. Scuseria, M.A. Robb, J.R. Cheeseman, G. Scalmani, V. Barone, B. Mennucci, G.A. Petersson, H. Nakatsuji, M. Caricato, X. Li, H.P. Hratchian, A.F. Izmaylov, J. Bloino, G. Zheng, J.L. Sonnenberg, M. Hada, M. Ehara, K. Toyota, R. Fukuda, J. Hasegawa, M. Ishida, T. Nakajima, Y. Honda, O. Kitao, H. Nakai, T. Vreven, J.A.J. Montgomery, J.E. Peralta, F. Ogliaro, M. Bearpark, J.J. Heyd, E. Brothers, K.N. Kudin, V.N. Staroverov, T. Keith, R. Kobayashi, J. Normand, K. Raghavachari, A. Rendell, J.C. Burant, S.S. Iyengar, J. Tomasi, M. Cossi, N. Rega, J.M. Millam, M. Klene, J.E. Knox, J.B. Cross, V. Bakken, C. Adamo, J. Jaramillo, R. Gomperts, R.E. Stratmann, O. Yazyev, A.J. Austin, R. Cammi, C. Pomelli, J.W. Ochterski, R.L. Martin, K. Morokuma, V.G. Zakrzewski, G.A. Voth, P. Salvador, J.J. Dannenberg, S. Dapprich, A.D. Daniels, O. Farkas, J.B. Foresman, J.V. Ortiz, J. Cioslowski, D.J. Fox, Gaussian, Inc., Wallingford CT, 2009. [10] M. Cossi, N. Rega, G. Scalmani, and V. Barone, J. Comput. Chem. 2003, 24, 669-81. [11] S. Grimme, S. Ehrlich, L. Goerigk, J. Comput. Chem. 2011, 32, 1456–1465. 21 Cartesian coordinates for all optimized structures including absolute energies and imaginary frequencies for transition states. Flavanone E = -729.205900764 a.u. C -4.221140 -0.095510 C -2.854391 -0.183367 -0.042386 C -2.054389 0.968134 -0.063759 C -2.659507 2.223375 0.131963 C -4.041968 2.318310 0.311152 C -4.809922 1.164005 0.316219 H -4.834780 -0.990446 0.161468 H -2.354860 -1.135284 -0.201046 C -0.621668 0.875624 -0.387386 H -4.483970 3.298430 0.456898 H -5.883911 1.243827 0.461212 C -0.544438 3.255019 0.392038 C 0.061990 2.218278 -0.544010 H 1.136131 2.111132 -0.372071 C 0.084376 4.612514 0.252785 C 1.326655 4.849713 0.846134 C -0.518771 5.624196 -0.494917 C 1.958589 6.078592 0.693248 H 1.798558 4.065673 1.436337 C 0.111650 6.856912 -0.641239 H -1.488663 5.442150 -0.946519 C 1.350795 7.087193 -0.050946 H 2.923194 6.251587 H -0.370185 7.641293 -1.218382 H 1.839803 8.050351 -0.165624 O -0.039936 -0.183801 -0.563255 O -1.956873 3.384862 0.149528 1.161998 0.148334 22 H -0.064722 2.558019 -1.581640 H -0.427648 2.897997 1.430162 23 [N4PyFe4+O]2+ (S=1) E = -2540.43900076 a.u. Fe 0.233644 0.003578 -0.032206 N 1.720951 0.462114 1.350460 N -0.880927 1.565177 0.652555 N -0.412188 -1.121506 1.445585 N 1.502954 -1.419683 -0.576535 N 1.273042 1.230530 -1.182559 C 0.993535 0.413330 2.666349 H 1.723998 0.339133 3.483816 C 0.140158 1.645978 2.939167 H -0.405751 1.446088 3.868458 H 0.787527 2.494243 3.193773 C -0.854820 2.096262 1.897928 C -1.721459 3.130456 2.253209 H -1.672201 3.529502 3.261883 C -2.624636 3.637736 1.332998 H -3.300891 4.440452 1.608228 C -2.641038 3.092249 0.053108 H -3.326112 3.446760 -0.708106 C -1.765834 2.066061 -0.244770 H -1.760178 1.589610 -1.218361 C 0.129552 -0.829464 2.648964 C -0.172050 -1.581008 3.775334 H 0.281489 -1.333649 4.730723 C -1.063871 -2.645081 3.656233 H -1.315746 -3.245938 4.523718 C -1.625221 -2.926676 2.414477 H -2.327371 -3.742168 2.285124 C -1.272120 -2.146692 1.322566 H -1.668544 -2.309656 0.324959 C 2.774655 -0.600047 1.307829 24 H 3.768597 -0.145718 1.384611 H 2.662761 -1.230161 2.198324 C 2.671269 -1.471955 0.093799 C 3.684116 -2.344969 -0.283783 H 4.617084 -2.360801 C 3.477859 -3.194149 -1.364902 H 4.255856 -3.883908 -1.675119 C 2.261095 -3.146130 -2.039996 H 2.056549 -3.793770 -2.884572 C 1.298032 -2.241072 -1.624990 H 0.335148 -2.138678 -2.115624 C 2.270950 1.783565 0.939136 H 3.268054 1.951859 1.361887 H 1.625719 2.573151 1.332138 C 2.270294 1.899639 -0.558997 C 3.153882 2.700202 -1.268803 H 3.948169 3.224019 -0.746856 C 2.997605 2.822482 -2.647109 H 3.675745 3.445802 -3.220508 C 1.965749 2.134029 -3.278023 H 1.813088 2.202995 -4.348847 C 1.126278 1.336223 -2.515384 H 0.310760 0.760060 -2.943317 O -0.877921 -0.444837 -1.138593 0.270963 25 [N4PyFe4+O]2++Flavanone E = -3270.63045564 a.u. Fe 0.19106500 -0.30279800 -1.03267800 N 1.12282400 0.42679500 N -0.96165100 1.36873200 -1.15572300 N -1.04461000 -1.09402600 N 1.41429100 -1.83951700 -0.79859200 N 1.66359800 C -0.01281900 0.69633400 1.56685100 H 0.38965200 0.80946500 2.58336400 C -0.79537700 1.96577000 1.25867500 H -1.61935700 2.00191100 1.98050400 H -0.18874200 2.84575400 1.50761000 C -1.36526700 2.14697200 -0.12399200 C -2.27319100 3.18902600 -0.31782500 H -2.57627400 3.78388700 C -2.77232800 3.45598900 -1.58250000 H -3.48842600 4.25707100 -1.73802300 C -2.33117600 2.67471900 -2.64548500 H -2.68327700 2.83748800 -3.65982600 C -1.43462800 1.65333400 -2.39536500 H -1.09203400 0.99284900 -3.18379200 C -0.91921200 -0.51325000 1.52150000 C -1.61517900 -0.96960500 2.63057200 H -1.48061700 -0.48378200 3.59270900 C -2.47636700 -2.05476000 2.48732500 H -3.03061700 -2.43202900 3.34053300 C -2.60265400 -2.64860700 1.23703700 H -3.25644400 -3.49916400 1.08103200 C -1.86974000 -2.14910900 0.16781200 H -1.93912800 -2.58778700 -0.82732600 C 2.02229400 -0.62499900 0.61497700 0.30360600 0.59786500 -2.00379100 0.53845000 1.19317500 26 H 2.96416400 -0.16995600 1.51888900 H 1.54757100 -1.02061800 2.09910600 C 2.26481700 -1.75915200 0.24473800 C 3.25603500 -2.70950200 0.45441600 H 3.92922300 -2.61106400 1.30033200 C 3.36272600 -3.77837500 -0.42750500 H 4.12834300 -4.53320000 -0.28280700 C 2.47460400 -3.86252600 -1.49531100 H 2.52108900 -4.68062500 -2.20469400 C 1.51870100 -2.87291500 -1.65864700 H 0.81372000 -2.86728100 -2.48362000 C 1.90273800 1.61311100 0.15951300 H 2.68778100 1.87742100 0.87751500 H 1.22609400 2.46934300 0.09746300 C 2.45293800 1.36383400 -1.21661200 C 3.62758700 1.92819100 -1.69178400 H 4.24436800 2.53448600 -1.03608100 C 3.99194800 1.70536600 -3.01764700 H 4.90673100 2.13537400 -3.41214000 C 3.17286000 0.92092000 -3.82310500 H 3.42517700 0.72317700 -4.85855900 C 2.01959200 0.37239200 -3.27890900 H 1.34086600 -0.26627000 -3.83725100 O -0.45558600 -0.96681100 -2.55528800 C -4.51504900 -5.46750600 -5.42639400 C -3.74043500 -4.71693500 -4.56671500 C -4.07746200 -3.38406700 -4.27586600 C -5.22487200 -2.81861100 -4.88137900 C -6.00872700 -3.58044300 -5.75591400 C -5.65197300 -4.88955800 -6.01978600 H -4.25323100 -6.49643000 -5.64755200 H -2.85387700 -5.12596100 -4.09215700 C -3.26280800 -2.58100600 -3.38229900 H -6.88174400 -3.12264700 -6.20752600 27 H -6.26373800 -5.47869900 -6.69595300 C -4.95994900 -0.68887000 -3.74777200 C -3.73319500 -1.25508500 -3.15000900 H -1.11697800 -1.69731300 -2.52622400 C -4.71661100 0.64521600 -4.42564500 C -3.74098600 0.75041600 -5.42216800 C -5.48237800 1.75964600 -4.08743000 C -3.54852700 1.95810500 -6.08463700 H -3.15325900 -0.12558900 -5.69243100 C -5.28401700 2.97239300 -4.74507500 H -6.25295300 1.67135600 -3.32460500 C -4.32107200 3.07138200 -5.74688500 H -2.80704100 2.03126200 -6.87464500 H -5.89752000 3.83185100 -4.49198000 H -4.18013400 4.00982100 -6.27466200 O -2.20797100 -3.02211400 -2.84587100 O -5.62847500 -1.54603200 -4.68862100 H -3.17291400 -0.60689900 -2.47626800 H -5.69751500 -0.51940900 -2.94125300 28 [N4PyFe4+O]2+ + Flavanone (TS1 from C2) E = -3270.60134020 a.u. Fe -0.450841 -0.276145 -1.224223 N 0.396398 0.205115 N -1.418966 1.500710 -1.222293 N -1.790917 -1.111331 -0.044330 N 0.670552 -1.922765 -1.058513 N 1.175420 C -0.794889 0.445976 1.490138 H -0.473785 0.430121 2.541262 C -1.488353 1.782502 1.257219 H -2.381603 1.783759 1.892188 H -0.870326 2.590338 1.670354 C -1.886956 2.173525 -0.143670 C -2.662127 3.323247 -0.293756 H -3.026690 3.828383 C -2.943160 3.818807 -1.557732 H -3.551336 4.709451 -1.678270 C -2.406830 3.161904 -2.659532 H -2.569605 3.509474 -3.674609 C -1.659497 2.019327 -2.448188 H -1.227588 1.474122 -3.279534 C -1.752151 -0.695660 1.240096 C -2.565698 -1.260822 2.210823 H -2.508940 -0.912038 3.237713 C -3.442379 -2.279474 1.843051 H -4.088878 -2.737766 2.584240 C -3.465546 -2.708799 0.519810 H -4.122428 -3.507517 0.193357 C -2.617908 -2.109166 -0.400222 H -2.568252 -2.409952 -1.443278 C 1.183271 -0.962860 0.603348 0.587482 -1.929398 0.595801 1.108046 29 H 2.123723 -0.617315 1.552070 H 0.619884 -1.429726 1.925020 C 1.435461 -1.995335 0.050175 C 2.363495 -3.012510 0.232634 H 2.969108 -3.036393 1.133280 C 2.497978 -3.990161 -0.747406 H 3.219041 -4.791818 -0.625465 C 1.698071 -3.916340 -1.883031 H 1.766959 -4.647949 -2.680708 C 0.800938 -2.866738 -2.009833 H 0.175749 -2.748361 -2.887949 C 1.275447 1.376416 0.339964 H 2.014216 1.512798 1.138855 H 0.660963 2.280112 0.317560 C 1.929308 1.225936 -1.004956 C 3.177048 1.742380 -1.322686 H 3.764298 2.245848 -0.561292 C 3.654683 1.602369 -2.623351 H 4.627862 1.998838 -2.893685 C 2.875939 0.936323 -3.564904 H 3.220182 0.794940 -4.582945 C 1.643446 0.429752 -3.180265 H 0.995017 -0.130203 -3.850281 O -1.086497 -0.851889 -2.725635 C -3.352616 -5.295817 -2.868590 C -2.344481 -4.647629 -3.565463 C -2.512812 -3.329778 -4.009542 C -3.710809 -2.659472 -3.703537 C -4.736429 -3.307209 -3.012743 C -4.554011 -4.624296 -2.611119 H -3.226261 -6.325501 -2.551314 H -1.413512 -5.148747 -3.819365 C -1.487806 -2.658204 -4.820557 H -5.655995 -2.769217 -2.805670 30 H -5.359475 -5.136651 -2.092995 C -2.858202 -0.594687 -4.534002 C -1.967459 -1.380200 -5.470999 H -1.100757 -0.796896 -5.785519 C -3.326658 0.737070 -4.952359 C -2.528725 1.547537 -5.781591 C -4.570678 1.234452 -4.524575 C -2.979870 2.792505 -6.203402 H -1.561739 1.191741 -6.128007 C -5.016019 2.479249 -4.949116 H -5.199023 0.620721 -3.889095 C -4.228557 3.262327 -5.794077 H -2.363803 3.390368 -6.867854 H -5.992239 2.835069 -4.633660 H -4.588401 4.226364 -6.139699 O -0.356815 -3.094571 -4.978097 O -3.922372 -1.348892 -4.012278 H -2.529968 -1.639431 -6.381317 H -2.003532 -0.493015 -3.473420 31 [N4PyFe3+OH] + Flavanone E = -3270.63297698 a.u. Fe -0.429350000 -0.284885000 -1.154024000 N 0.422382000 0.189000000 0.643123000 N -1.420173000 1.473350000 -1.190572000 N -1.771467000 -1.121671000 0.027191000 N 0.670332000 -1.927413000 -1.032380000 N 1.189041000 0.574933000 -1.887588000 C -0.761992000 0.443112000 1.537726000 H -0.430654000 0.442529000 2.585797000 C -1.457163000 1.777658000 1.289149000 H -2.341097000 1.789606000 1.936930000 H -0.833911000 2.591902000 1.681312000 C -1.879652000 2.150963000 -0.111295000 C -2.674973000 3.288020000 -0.259263000 H -3.033211000 3.795605000 0.631508000 C -2.987377000 3.766875000 -1.522163000 H -3.612899000 4.645796000 -1.639664000 C -2.459106000 3.108917000 -2.628094000 H -2.644915000 3.444075000 -3.643591000 C -1.689312000 1.981419000 -2.418346000 H -1.257624000 1.447112000 -3.259283000 C -1.722331000 -0.700916000 1.309279000 C -2.526976000 -1.262114000 2.289290000 H -2.462417000 -0.910360000 3.314687000 C -3.405970000 -2.282520000 1.930825000 H -4.045684000 -2.739491000 2.678705000 C -3.442020000 -2.715176000 0.608736000 H -4.102856000 -3.514719000 0.293014000 C -2.603036000 -2.119302000 -0.322132000 H -2.565675000 -2.420663000 -1.367269000 C 1.202787000 -0.990984000 1.138556000 32 H 2.145228000 -0.654863000 1.585159000 H 0.635200000 -1.460038000 1.951250000 C 1.446687000 -2.013981000 0.068158000 C 2.376791000 -3.032529000 0.226842000 H 2.991783000 -3.070381000 1.120605000 C 2.503120000 -3.994237000 -0.770926000 H 3.226658000 -4.796357000 -0.668396000 C 1.693563000 -3.903740000 -1.898339000 H 1.758839000 -4.621372000 -2.708996000 C 0.791594000 -2.854628000 -2.000165000 H 0.158084000 -2.728153000 -2.872552000 C 1.311184000 1.354558000 0.379300000 H 2.050796000 1.483418000 1.178413000 H 0.701821000 2.261819000 0.358707000 C 1.959034000 1.200539000 -0.967997000 C 3.210531000 1.701604000 -1.294040000 H 3.811355000 2.195024000 -0.536636000 C 3.674091000 1.559545000 -2.599934000 H 4.650054000 1.943717000 -2.877844000 C 2.877779000 0.908526000 -3.537168000 H 3.210427000 0.768005000 -4.559175000 C 1.642018000 0.415948000 -3.143473000 H 0.981924000 -0.130243000 -3.813565000 O -1.183638000 -0.860109000 -2.687203000 C -3.267981000 -5.163284000 -2.737937000 C -2.277535000 -4.522499000 -3.463796000 C -2.512702000 -3.269552000 -4.048993000 C -3.768179000 -2.667986000 -3.863849000 C -4.775323000 -3.303167000 -3.137781000 C -4.520993000 -4.552254000 -2.588224000 H -3.089046000 -6.145696000 -2.313912000 H -1.306250000 -4.980972000 -3.631451000 C -1.495286000 -2.600849000 -4.862880000 H -5.737957000 -2.815071000 -3.026796000 33 H -5.311039000 -5.063187000 -2.045584000 C -3.119963000 -0.693055000 -5.016097000 C -2.006328000 -1.425793000 -5.673661000 H -1.167732000 -0.762326000 -5.896214000 C -3.462326000 0.671957000 -5.233857000 C -2.629165000 1.521074000 -6.008607000 C -4.665663000 1.219602000 -4.714401000 C -3.000801000 2.829716000 -6.273819000 H -1.706922000 1.137356000 -6.435991000 C -5.025674000 2.526628000 -4.993862000 H -5.324103000 0.589105000 -4.127109000 C -4.204162000 3.341978000 -5.779001000 H -2.360549000 3.451504000 -6.892087000 H -5.966615000 2.913157000 -4.613471000 H -4.503352000 4.358439000 -6.014593000 O -0.330557000 -2.968593000 -4.931076000 O -4.055268000 -1.414363000 -4.324972000 H -2.334704000 -1.825995000 -6.649692000 H -1.958157000 -0.350483000 -2.977379000 34 [N4PyFe2+] + 2-hydroxy flavanone (TS2 from C2) E = -3270.61447909 a.u. Fe -0.649887000 -0.043072000 -1.225569000 N 0.424830000 0.454257000 0.603823000 N -1.225326000 1.856523000 -1.434950000 N -2.109576000 -0.417604000 0.174641000 N 0.033208000 -1.841057000 -0.854785000 N 1.223182000 0.379968000 -1.991113000 C -0.656641000 1.036268000 1.440367000 H -0.325242000 1.116941000 2.487882000 C -1.075682000 2.442952000 1.012469000 H -1.949899000 2.702973000 1.621130000 H -0.308904000 3.157409000 1.337348000 C -1.398306000 2.756380000 -0.432780000 C -1.812609000 4.062699000 -0.701306000 H -1.946307000 4.747836000 0.130753000 C -2.029829000 4.484534000 -2.002875000 H -2.344477000 5.501883000 -2.210117000 C -1.813580000 3.571721000 -3.030772000 H -1.945886000 3.844199000 -4.071883000 C -1.421702000 2.288683000 -2.706887000 H -1.262473000 1.537391000 -3.473292000 C -1.845822000 0.098256000 1.391826000 C -2.637208000 -0.186399000 2.496673000 H -2.391612000 0.241608000 3.464605000 C -3.736509000 -1.027019000 2.340347000 H -4.369162000 -1.266449000 3.188629000 C -3.999108000 -1.566244000 1.084474000 H -4.836163000 -2.236829000 0.925804000 C -3.158567000 -1.245240000 0.028328000 H -3.292463000 -1.652367000 -0.972539000 C 0.950060000 -0.812188000 1.169028000 35 H 2.001439000 -0.687698000 1.456999000 H 0.416413000 -1.034047000 2.102245000 C 0.806570000 -1.993730000 0.244620000 C 1.402741000 -3.211939000 0.549983000 H 2.026073000 -3.296011000 1.435223000 C 1.185405000 -4.308479000 -0.275612000 H 1.644022000 -5.265562000 -0.050013000 C 0.363691000 -4.154119000 -1.387880000 H 0.149709000 -4.981513000 -2.055705000 C -0.188116000 -2.910641000 -1.642617000 H -0.846325000 -2.729955000 -2.483932000 C 1.512391000 1.359875000 0.192914000 H 2.284992000 1.456251000 0.968165000 H 1.100006000 2.359583000 0.031782000 C 2.107252000 0.898502000 -1.110961000 C 3.451240000 1.046734000 -1.423167000 H 4.134438000 1.460878000 -0.687891000 C 3.901009000 0.659797000 -2.683161000 H 4.948166000 0.764805000 -2.947733000 C 2.989487000 0.126408000 -3.587713000 H 3.293348000 -0.203458000 -4.574829000 C 1.663212000 -0.004885000 -3.201274000 H 0.930201000 -0.454425000 -3.866588000 O -1.895056000 -0.609342000 -2.787111000 C -1.801240000 -5.830859000 -4.363296000 C -1.030713000 -4.733013000 -4.713446000 C -1.591460000 -3.448739000 -4.720204000 C -2.929996000 -3.301280000 -4.339786000 C -3.710565000 -4.385978000 -3.966060000 C -3.138102000 -5.653321000 -3.990256000 H -1.374860000 -6.828198000 -4.389240000 H 0.009704000 -4.833527000 -5.010955000 C -0.808466000 -2.264911000 -5.081455000 H -4.744391000 -4.231386000 -3.676504000 36 H -3.742531000 -6.512360000 -3.718125000 C -2.871908000 -0.944435000 -4.582775000 C -1.648672000 -1.054076000 -5.420318000 H -1.048583000 -0.145285000 -5.363287000 C -3.721461000 0.241091000 -4.607175000 C -3.412210000 1.331505000 -5.436270000 C -4.874695000 0.293353000 -3.803277000 C -4.249666000 2.439576000 -5.471405000 H -2.539222000 1.304351000 -6.082556000 C -5.693246000 1.412492000 -3.828773000 H -5.127293000 -0.555729000 -3.174606000 C -5.385167000 2.486737000 -4.664754000 H -4.022105000 3.264078000 -6.140096000 H -6.584111000 1.443409000 -3.210105000 H -6.037815000 3.353307000 -4.697021000 O 0.410252000 -2.244723000 -5.130743000 O -3.544399000 -2.058313000 -4.284960000 H -1.966049000 -1.165232000 -6.470441000 H -2.628389000 -0.025458000 -2.552016000 37 [N4PyFe2+] + 2-hydroxy flavanone (product, from C2) E = -3270.64024968 a.u. Fe -0.459293000 -0.124164000 -1.268842000 N 0.440623000 0.435472000 0.607669000 N -1.107822000 1.729543000 -1.578744000 N -2.013173000 -0.581431000 -0.006409000 N 0.267947000 -1.897393000 -0.850704000 N 1.370034000 0.341272000 -1.977182000 C -0.734558000 0.992170000 1.330211000 H -0.499395000 1.105874000 2.400224000 C -1.183183000 2.370360000 0.844295000 H -2.085114000 2.617889000 1.416057000 H -0.452337000 3.120560000 1.172804000 C -1.463029000 2.621179000 -0.619207000 C -2.009763000 3.859517000 -0.958558000 H -2.300899000 4.538124000 -0.162235000 C -2.153813000 4.226926000 -2.287173000 H -2.576260000 5.190714000 -2.551542000 C -1.715256000 3.342027000 -3.267778000 H -1.773447000 3.584765000 -4.322458000 C -1.213730000 2.118161000 -2.873945000 H -0.880553000 1.387991000 -3.605231000 C -1.869941000 -0.004255000 1.208263000 C -2.721385000 -0.292931000 2.265853000 H -2.568215000 0.189148000 3.227145000 C -3.755114000 -1.205819000 2.077687000 H -4.433530000 -1.444741000 2.890089000 C -3.885840000 -1.820494000 0.836697000 H -4.660399000 -2.555690000 0.651067000 C -2.993574000 -1.493201000 -0.173226000 H -3.043737000 -1.966260000 -1.151243000 C 0.957818000 -0.800789000 1.237125000 38 H 1.984135000 -0.640010000 1.590366000 H 0.370733000 -1.016187000 2.138972000 C 0.917629000 -2.008535000 0.332364000 C 1.506236000 -3.204807000 0.725199000 H 2.023688000 -3.259785000 1.678493000 C 1.424030000 -4.316280000 -0.104767000 H 1.877878000 -5.256590000 0.190436000 C 0.751899000 -4.198133000 -1.317600000 H 0.658846000 -5.034563000 -2.001158000 C 0.193126000 -2.976946000 -1.654757000 H -0.332938000 -2.836808000 -2.593693000 C 1.514544000 1.366333000 0.218436000 H 2.254781000 1.499282000 1.018998000 H 1.076764000 2.350732000 0.029938000 C 2.182755000 0.912637000 -1.055849000 C 3.531495000 1.119481000 -1.305810000 H 4.156639000 1.571863000 -0.541962000 C 4.062110000 0.742517000 -2.536869000 H 5.114991000 0.895611000 -2.749933000 C 3.223747000 0.158164000 -3.479461000 H 3.593512000 -0.162972000 -4.446390000 C 1.886795000 -0.037390000 -3.162302000 H 1.211577000 -0.529895000 -3.862121000 O -2.188948000 -0.644672000 -2.968164000 C -2.037296000 -5.706034000 -4.280888000 C -1.241598000 -4.618138000 -4.589841000 C -1.779082000 -3.320258000 -4.595427000 C -3.129768000 -3.135205000 -4.253713000 C -3.933741000 -4.226473000 -3.932877000 C -3.385507000 -5.502454000 -3.959794000 H -1.630606000 -6.711392000 -4.306003000 H -0.195931000 -4.731946000 -4.865604000 C -0.962587000 -2.163376000 -4.954112000 H -4.975957000 -4.060702000 -3.680930000 39 H -4.018053000 -6.353251000 -3.726088000 C -2.867635000 -0.755473000 -4.261541000 C -1.770259000 -0.931348000 -5.286179000 H -1.122143000 -0.052659000 -5.328351000 C -3.773683000 0.438905000 -4.429916000 C -3.619093000 1.366345000 -5.459123000 C -4.779562000 0.633637000 -3.474222000 C -4.454113000 2.480869000 -5.525195000 H -2.858611000 1.226276000 -6.222968000 C -5.602291000 1.751777000 -3.534477000 H -4.946426000 -0.119137000 -2.704067000 C -5.437180000 2.680800000 -4.560578000 H -4.338011000 3.190215000 -6.339027000 H -6.387055000 1.887672000 -2.797058000 H -6.087565000 3.547787000 -4.618821000 O 0.263523000 -2.170043000 -4.966272000 O -3.714800000 -1.896404000 -4.194933000 H -2.227918000 -1.062068000 -6.274029000 H -2.802850000 -0.137376000 -2.415939000 40 [N4PyFe4+O]2+ + Flavanone (TS1 from C3) E = -3270.58120434 a.u. Fe 0.047258000 -0.192076000 -1.305379000 N 0.770304000 0.317850000 0.539598000 N -1.118229000 1.486279000 -1.297422000 N -1.275905000 -1.181998000 -0.221853000 N 1.251481000 -1.750530000 -1.133665000 N 1.634735000 0.834955000 -1.932517000 C -0.467714000 0.424077000 1.391404000 H -0.178850000 0.389319000 2.451090000 C -1.252843000 1.710889000 1.184618000 H -2.149626000 1.629764000 1.809176000 H -0.703567000 2.555547000 1.619956000 C -1.674333000 2.081136000 -0.213420000 C -2.592879000 3.121359000 -0.352816000 H -3.020421000 3.562606000 0.542588000 C -2.945170000 3.582687000 -1.611494000 H -3.671296000 4.381078000 -1.726523000 C -2.339663000 3.001117000 -2.719153000 H -2.569588000 3.315390000 -3.732582000 C -1.442492000 1.968741000 -2.522918000 H -0.967358000 1.472466000 -3.360675000 C -1.325270000 -0.777813000 1.068511000 C -2.129560000 -1.414927000 2.001491000 H -2.140956000 -1.071620000 3.031810000 C -2.906035000 -2.498435000 1.596369000 H -3.546857000 -3.008996000 2.307758000 C -2.821785000 -2.932622000 0.277878000 H -3.384326000 -3.790276000 -0.074112000 C -1.982781000 -2.261477000 -0.600317000 H -1.822460000 -2.599902000 -1.618061000 C 1.654749000 -0.784066000 1.045374000 41 H 2.554067000 -0.356784000 1.502261000 H 1.124166000 -1.304100000 1.851972000 C 2.004764000 -1.783837000 -0.015532000 C 2.982090000 -2.752166000 0.171429000 H 3.582559000 -2.748379000 1.075636000 C 3.161974000 -3.724732000 -0.806487000 H 3.918585000 -4.492078000 -0.680552000 C 2.351339000 -3.705600000 -1.936813000 H 2.443393000 -4.457321000 -2.711986000 C 1.407489000 -2.699385000 -2.079410000 H 0.735088000 -2.636970000 -2.931893000 C 1.547254000 1.573875000 0.347460000 H 2.215221000 1.766109000 1.195095000 H 0.848909000 2.412704000 0.291622000 C 2.288858000 1.503939000 -0.955133000 C 3.506519000 2.126059000 -1.187753000 H 4.010768000 2.650775000 -0.382739000 C 4.059544000 2.065936000 -2.464554000 H 5.011190000 2.544783000 -2.670735000 C 3.379873000 1.380298000 -3.465671000 H 3.780158000 1.308106000 -4.470412000 C 2.173037000 0.766314000 -3.161755000 H 1.597623000 0.198740000 -3.887244000 O -0.359754000 -0.609154000 -2.932393000 C -5.030543000 -5.484148000 -3.307261000 C -3.797910000 -4.863579000 -3.316636000 C -3.678731000 -3.511569000 -3.689816000 C -4.837729000 -2.797927000 -4.066280000 C -6.083250000 -3.431057000 -4.072907000 C -6.169762000 -4.761711000 -3.697200000 H -5.120725000 -6.526507000 -3.020676000 H -2.886313000 -5.398622000 -3.064034000 C -2.362919000 -2.895798000 -3.841805000 H -6.957565000 -2.866679000 -4.377707000 42 H -7.139389000 -5.250720000 -3.706564000 C -3.649686000 -0.727756000 -4.023632000 C -2.372093000 -1.472699000 -4.242812000 H -1.334028000 -0.955582000 -3.368826000 C -3.788852000 0.626564000 -4.669136000 C -2.886449000 1.127753000 -5.608752000 C -4.906316000 1.396305000 -4.326912000 C -3.101146000 2.372033000 -6.202325000 H -2.013272000 0.551593000 -5.903903000 C -5.125302000 2.634247000 -4.919209000 H -5.620231000 1.002070000 -3.607410000 C -4.222105000 3.125197000 -5.862902000 H -2.400676000 2.742494000 -6.944556000 H -6.006821000 3.211730000 -4.657506000 H -4.397209000 4.085566000 -6.338075000 O -1.301526000 -3.503689000 -3.643006000 O -4.804263000 -1.503363000 -4.461719000 H -1.801595000 -1.278111000 -5.153091000 H -3.793573000 -0.615573000 -2.929366000 43 [N4PyFe3+OH]2+ + Flavanone (product, from C3) E = -3270.61016092 a.u. Fe 0.191065000 -0.302798000 -1.032678000 N 1.122824000 0.426795000 0.614977000 N -0.961651000 1.368732000 -1.155723000 N -1.044610000 -1.094026000 0.303606000 N 1.414291000 -1.839517000 -0.798592000 N 1.663598000 0.597865000 -2.003791000 C -0.012819000 0.696334000 1.566851000 H 0.389652000 0.809465000 2.583364000 C -0.795377000 1.965770000 1.258675000 H -1.619357000 2.001911000 1.980504000 H -0.188742000 2.845754000 1.507610000 C -1.365267000 2.146972000 -0.123992000 C -2.273191000 3.189026000 -0.317825000 H -2.576274000 3.783887000 0.538450000 C -2.772328000 3.455989000 -1.582500000 H -3.488426000 4.257071000 -1.738023000 C -2.331176000 2.674719000 -2.645485000 H -2.683277000 2.837488000 -3.659826000 C -1.434628000 1.653334000 -2.395365000 H -1.092034000 0.992849000 -3.183792000 C -0.919212000 -0.513250000 1.521500000 C -1.615179000 -0.969605000 2.630572000 H -1.480617000 -0.483782000 3.592709000 C -2.476367000 -2.054760000 2.487325000 H -3.030617000 -2.432029000 3.340533000 C -2.602654000 -2.648607000 1.237037000 H -3.256444000 -3.499164000 1.081032000 C -1.869740000 -2.149109000 0.167812000 H -1.939128000 -2.587787000 -0.827326000 C 2.022294000 -0.624999000 1.193175000 44 H 2.964164000 -0.169956000 1.518889000 H 1.547571000 -1.020618000 2.099106000 C 2.264817000 -1.759152000 0.244738000 C 3.256035000 -2.709502000 0.454416000 H 3.929223000 -2.611064000 1.300332000 C 3.362726000 -3.778375000 -0.427505000 H 4.128343000 -4.533200000 -0.282807000 C 2.474604000 -3.862526000 -1.495311000 H 2.521089000 -4.680625000 -2.204694000 C 1.518701000 -2.872915000 -1.658647000 H 0.813720000 -2.867281000 -2.483620000 C 1.902738000 1.613111000 0.159513000 H 2.687781000 1.877421000 0.877515000 H 1.226094000 2.469343000 0.097463000 C 2.452938000 1.363834000 -1.216612000 C 3.627587000 1.928191000 -1.691784000 H 4.244368000 2.534486000 -1.036081000 C 3.991948000 1.705366000 -3.017647000 H 4.906731000 2.135374000 -3.412140000 C 3.172860000 0.920920000 -3.823105000 H 3.425177000 0.723177000 -4.858559000 C 2.019592000 0.372392000 -3.278909000 H 1.340866000 -0.266270000 -3.837251000 O -0.455586000 -0.966811000 -2.555288000 C -4.515049000 -5.467506000 -5.426394000 C -3.740435000 -4.716935000 -4.566715000 C -4.077462000 -3.384067000 -4.275866000 C -5.224872000 -2.818611000 -4.881379000 C -6.008727000 -3.580443000 -5.755914000 C -5.651973000 -4.889558000 -6.019786000 H -4.253231000 -6.496430000 -5.647552000 H -2.853877000 -5.125961000 -4.092157000 C -3.262808000 -2.581006000 -3.382299000 H -6.881744000 -3.122647000 -6.207526000 45 H -6.263738000 -5.478699000 -6.695953000 C -4.959949000 -0.688870000 -3.747772000 C -3.733195000 -1.255085000 -3.150009000 H -1.116978000 -1.697313000 -2.526224000 C -4.716611000 0.645216000 -4.425645000 C -3.740986000 0.750416000 -5.422168000 C -5.482378000 1.759646000 -4.087430000 C -3.548527000 1.958105000 -6.084637000 H -3.153259000 -0.125589000 -5.692431000 C -5.284017000 2.972393000 -4.745075000 H -6.252953000 1.671356000 -3.324605000 C -4.321072000 3.071382000 -5.746885000 H -2.807041000 2.031262000 -6.874645000 H -5.897520000 3.831851000 -4.491980000 H -4.180134000 4.009821000 -6.274662000 O -2.207971000 -3.022114000 -2.845871000 O -5.628475000 -1.546032000 -4.688621000 H -3.172914000 -0.606899000 -2.476268000 H -5.697515000 -0.519409000 -2.941253000 46 N4PyFe 2+ + 3-hydroxy-flavanone (TS2, from C3) E = -3270.58975061 a.u. Fe -0.784043000 -0.192742000 -0.956966000 N 0.947994000 0.218612000 0.163412000 N -1.455005000 1.715609000 -0.559399000 N -1.433503000 -0.886549000 0.784162000 N 0.154945000 -1.951313000 -1.269989000 N 0.280775000 0.481896000 -2.457873000 C 0.368097000 0.590560000 1.495591000 H 1.153042000 0.529731000 2.263724000 C -0.190838000 2.005898000 1.568032000 H -0.627015000 2.116115000 2.567443000 H 0.638050000 2.725700000 1.560744000 C -1.207677000 2.450772000 0.549300000 C -1.815529000 3.691534000 0.744386000 H -1.595900000 4.247716000 1.650783000 C -2.673176000 4.206589000 -0.214164000 H -3.149510000 5.170463000 -0.067531000 C -2.892496000 3.465852000 -1.371145000 H -3.532925000 3.823261000 -2.169920000 C -2.272522000 2.237737000 -1.506533000 H -2.432262000 1.623697000 -2.387745000 C -0.698196000 -0.434612000 1.829775000 C -0.921220000 -0.872446000 3.127092000 H -0.305288000 -0.492411000 3.937292000 C -1.928333000 -1.803542000 3.368412000 H -2.121334000 -2.156337000 4.376143000 C -2.660833000 -2.288858000 2.291423000 H -3.437403000 -3.033165000 2.423703000 C -2.377750000 -1.820696000 1.016379000 H -2.910457000 -2.219876000 0.153286000 C 1.768797000 -1.017069000 0.277332000 47 H 2.833410000 -0.774335000 0.175577000 H 1.648454000 -1.417456000 1.291481000 C 1.370068000 -2.084951000 -0.702613000 C 2.176715000 -3.187018000 -0.962152000 H 3.153478000 -3.262412000 -0.494057000 C 1.713182000 -4.182161000 -1.815652000 H 2.328146000 -5.050139000 -2.029039000 C 0.453161000 -4.042758000 -2.390480000 H 0.043635000 -4.790086000 -3.061514000 C -0.290360000 -2.910972000 -2.099868000 H -1.268466000 -2.738447000 -2.532343000 C 1.640725000 1.273979000 -0.615395000 H 2.703081000 1.343584000 -0.349911000 H 1.193387000 2.242007000 -0.375580000 C 1.464129000 1.037233000 -2.093209000 C 2.411267000 1.409062000 -3.035707000 H 3.352065000 1.844255000 -2.713232000 C 2.137648000 1.213434000 -4.387387000 H 2.865743000 1.498324000 -5.139728000 C 0.926423000 0.637332000 -4.752949000 H 0.679703000 0.456886000 -5.793525000 C 0.028262000 0.271524000 -3.760502000 H -0.920988000 -0.206510000 -3.990541000 O -2.427145000 -0.672404000 -1.909445000 C -2.636180000 -5.689969000 -4.523301000 C -3.262075000 -4.889945000 -3.584981000 C -3.303945000 -3.495277000 -3.750602000 C -2.686372000 -2.921362000 -4.882119000 C -2.027600000 -3.722000000 -5.812706000 C -2.015297000 -5.098964000 -5.632809000 H -2.627554000 -6.768426000 -4.407105000 H -3.737170000 -5.308818000 -2.702578000 C -3.850926000 -2.629070000 -2.708750000 H -1.559545000 -3.257188000 -6.673914000 48 H -1.526680000 -5.724294000 -6.374029000 C -3.727209000 -0.835503000 -4.491974000 C -3.944406000 -1.211105000 -3.071145000 H -3.027491000 -0.921472000 -1.191818000 C -3.573104000 0.636023000 -4.781385000 C -2.581539000 1.112927000 -5.638769000 C -4.499843000 1.535233000 -4.243730000 C -2.489192000 2.474945000 -5.918022000 H -1.898480000 0.410869000 -6.105691000 C -4.421952000 2.890982000 -4.545715000 H -5.311413000 1.177846000 -3.612813000 C -3.406336000 3.367822000 -5.372510000 H -1.712921000 2.833775000 -6.587687000 H -5.169414000 3.572891000 -4.149792000 H -3.349195000 4.424701000 -5.613118000 O -4.116920000 -3.002376000 -1.559190000 O -2.645849000 -1.567603000 -5.076793000 H -4.678115000 -0.624928000 -2.523218000 H -4.654207000 -1.181691000 -4.998022000 49 N4PyFe 2+ + 3-hydroxy-flavanone (product, from C3) E = -3270.61858851 a.u. Fe -0.706406890 -0.104330791 -0.967448842 N 1.043611290 0.233822426 0.225253156 N -1.408482740 1.764958629 -0.592822212 N -1.432325090 -0.807019160 0.724980525 N 0.169543500 -1.873036991 -1.295790239 N 0.390913100 0.574584091 -2.424722990 C 0.396745910 0.603770106 1.517188194 H 1.120324110 0.539915139 2.336608888 C -0.164006750 2.025159035 1.563889759 H -0.635715590 2.135347799 2.549377433 H 0.663294490 2.741281054 1.587518687 C -1.156897940 2.493125362 0.521016733 C -1.739965870 3.747991784 0.703776097 H -1.510687750 4.303705976 1.609692351 C -2.570259720 4.278485118 -0.262709008 H -3.031605940 5.252759442 -0.121405051 C -2.809199320 3.541288023 -1.420902213 H -3.429336040 3.910188263 -2.225098266 C -2.208916510 2.304125691 -1.550668217 H -2.354492690 1.699905399 -2.441284148 C -0.707079670 -0.408798376 1.796680911 C -0.951034090 -0.883878435 3.075219860 H -0.335871290 -0.547136562 3.903886365 C -1.984232010 -1.797113524 3.275911962 H -2.196124600 -2.180189363 4.268770594 C -2.725442180 -2.222187881 2.175510135 H -3.526573300 -2.949207882 2.272858910 C -2.419567540 -1.717823753 0.920429047 H -2.949928350 -2.069079413 0.038388294 C 1.783788840 -1.040098962 0.323110169 50 H 2.867524940 -0.858266288 0.222249285 H 1.650699160 -1.449091919 1.331905570 C 1.341593240 -2.080239476 -0.678239834 C 2.094777330 -3.225203901 -0.924274705 H 3.047817950 -3.364009533 -0.419335687 C 1.615199640 -4.180144115 -1.812743970 H 2.184580500 -5.079674830 -2.012070471 C 0.390685090 -3.959622027 -2.445791410 H -0.027187800 -4.672240337 -3.149631114 C -0.291465810 -2.790435265 -2.166710367 H -1.231331960 -2.553076805 -2.649635196 C 1.767560290 1.271676182 -0.534149282 H 2.838409130 1.303229587 -0.273020099 H 1.357117980 2.251336578 -0.273003723 C 1.591092660 1.087101020 -2.023174716 C 2.558755760 1.477168075 -2.940841611 H 3.503985700 1.875896612 -2.589254315 C 2.295071010 1.351291142 -4.302869437 H 3.038864190 1.655151630 -5.033393888 C 1.079344340 0.821468895 -4.707590383 H 0.837721320 0.697576298 -5.757638708 C 0.150497000 0.432078655 -3.741128064 H -0.796742620 -0.012026440 -4.006453690 O -3.030477950 -0.605163689 -2.087366028 C -2.731129030 -5.781311135 -4.660407939 C -3.330228870 -5.017771691 -3.674282955 C -3.301393840 -3.613786486 -3.745323435 C -2.630763440 -2.995780581 -4.825806474 C -2.004292030 -3.761783308 -5.800210965 C -2.062524590 -5.147617723 -5.716386590 H -2.780182130 -6.864081236 -4.620711380 H -3.843421520 -5.474544226 -2.829462743 C -3.777623450 -2.786301322 -2.642457446 H -1.495896140 -3.264966422 -6.619785078 51 H -1.596301260 -5.745683060 -6.492219864 C -3.682592820 -0.949860435 -4.373337590 C -3.880817620 -1.270645572 -2.892508572 H -3.444218640 -0.519258562 -1.219330879 C -3.587848030 0.516496375 -4.694316734 C -2.657778680 1.006175716 -5.607531284 C -4.506774300 1.405785710 -4.120771227 C -2.618801670 2.364035075 -5.917520936 H -1.974972430 0.314271436 -6.091349841 C -4.488340550 2.756273207 -4.454205266 H -5.268092810 1.041109204 -3.427914639 C -3.529848730 3.242829070 -5.344845846 H -1.882141910 2.730586821 -6.631608326 H -5.225578860 3.427043656 -4.029193204 H -3.511523680 4.295546301 -5.608843644 O -3.974786700 -3.200729839 -1.505038094 O -2.534962120 -1.633161516 -4.905311191 H -4.921492110 -1.010819114 -2.666596533 H -4.561060850 -1.379223234 -4.880684631 52 N4PyFe 2+ OH2 + flavone (TS2, mechanism(2)) E = -3270.54878466 a.u. Fe 0.110605000 -0.264125000 -1.103629000 N 1.022204000 0.385311000 0.543563000 N -1.018656000 1.405923000 -1.191654000 N -1.103656000 -1.125300000 0.181297000 N 1.331266000 -1.829466000 -0.977892000 N 1.575954000 0.662092000 -2.048667000 C -0.112224000 0.611563000 1.513136000 H 0.297128000 0.697189000 2.529796000 C -0.920536000 1.875932000 1.251038000 H -1.746292000 1.869575000 1.971627000 H -0.329710000 2.756850000 1.534540000 C -1.479662000 2.110069000 -0.128747000 C -2.400458000 3.145975000 -0.286536000 H -2.750760000 3.673922000 0.595527000 C -2.843451000 3.503792000 -1.550502000 H -3.567247000 4.302114000 -1.679951000 C -2.319405000 2.827877000 -2.646814000 H -2.606232000 3.075937000 -3.664145000 C -1.420318000 1.802006000 -2.425090000 H -0.992424000 1.261936000 -3.262683000 C -0.999954000 -0.605772000 1.426618000 C -1.688373000 -1.134423000 2.507328000 H -1.570169000 -0.695869000 3.493851000 C -2.520794000 -2.232918000 2.302575000 H -3.069899000 -2.667658000 3.131206000 C -2.619059000 -2.771515000 1.024260000 H -3.241614000 -3.636005000 0.824034000 C -1.891935000 -2.199536000 -0.010897000 H -1.910469000 -2.608128000 -1.018553000 C 1.924034000 -0.689127000 1.074182000 53 H 2.863439000 -0.249958000 1.427835000 H 1.446573000 -1.131863000 1.956430000 C 2.179409000 -1.775290000 0.073445000 C 3.193891000 -2.706460000 0.257770000 H 3.855640000 -2.620662000 1.114170000 C 3.341917000 -3.739590000 -0.659037000 H 4.124877000 -4.479726000 -0.533190000 C 2.469159000 -3.801266000 -1.739784000 H 2.544041000 -4.585988000 -2.483480000 C 1.490505000 -2.829182000 -1.869886000 H 0.814525000 -2.847775000 -2.717367000 C 1.796117000 1.596476000 0.151682000 H 2.575658000 1.832539000 0.885615000 H 1.112652000 2.449236000 0.125811000 C 2.354015000 1.410339000 -1.230291000 C 3.524491000 2.007124000 -1.675160000 H 4.127258000 2.596223000 -0.991186000 C 3.904577000 1.839996000 -3.004282000 H 4.815836000 2.297305000 -3.375247000 C 3.102841000 1.073305000 -3.843775000 H 3.365036000 0.916047000 -4.883809000 C 1.953451000 0.492230000 -3.328378000 H 1.295998000 -0.128482000 -3.929915000 O -0.706005000 -0.925804000 -2.726906000 C -4.931251000 -5.500226000 -4.906812000 C -3.902801000 -4.796394000 -4.317316000 C -4.028249000 -3.415355000 -4.077437000 C -5.225388000 -2.752873000 -4.447980000 C -6.263173000 -3.473227000 -5.052968000 C -6.110867000 -4.828871000 -5.275113000 H -4.831537000 -6.564087000 -5.092963000 H -2.973387000 -5.277548000 -4.030667000 C -2.931986000 -2.661988000 -3.484638000 H -7.167754000 -2.945440000 -5.333312000 54 H -6.919923000 -5.380718000 -5.743543000 C -4.478899000 -0.605132000 -3.561996000 C -3.204975000 -1.272342000 -3.294736000 H -0.850878000 -1.916026000 -2.833089000 C -4.360736000 0.686918000 -4.337499000 C -3.402036000 0.826596000 -5.345478000 C -5.254338000 1.728340000 -4.085984000 C -3.342151000 1.997157000 -6.096000000 H -2.716187000 0.005537000 -5.550579000 C -5.196881000 2.898743000 -4.837575000 H -6.007966000 1.613232000 -3.309924000 C -4.240993000 3.034099000 -5.843925000 H -2.606594000 2.096711000 -6.888515000 H -5.906217000 3.699065000 -4.649396000 H -4.204208000 3.940974000 -6.439558000 O -1.832421000 -3.205432000 -3.175719000 O -5.448823000 -1.438134000 -4.272323000 H -1.710227000 -0.680921000 -2.912804000 H -4.969665000 -0.381533000 -2.596948000 55 N4PyFe 2+ OH2 + flavone (product, mechanism(2)) E = -3270.55086281 a.u. Fe 0.177175000 -0.202935000 -1.060814000 N 1.063993000 0.428026000 0.592533000 N -0.913797000 1.481619000 -1.184337000 N -1.095036000 -1.028565000 0.200638000 N 1.334907000 -1.794316000 -0.916626000 N 1.677797000 0.655337000 -1.988257000 C -0.076756000 0.683910000 1.542325000 H 0.313812000 0.773424000 2.566613000 C -0.865167000 1.955890000 1.253860000 H -1.690782000 1.978225000 1.974048000 H -0.261190000 2.834798000 1.516632000 C -1.419136000 2.170195000 -0.131011000 C -2.369158000 3.177431000 -0.305975000 H -2.758365000 3.687975000 0.570089000 C -2.793919000 3.529348000 -1.577753000 H -3.543048000 4.301318000 -1.720204000 C -2.205352000 2.891242000 -2.665595000 H -2.466593000 3.147130000 -3.687470000 C -1.279450000 1.895040000 -2.424344000 H -0.771492000 1.410653000 -3.253565000 C -0.988201000 -0.514648000 1.449549000 C -1.693458000 -1.024187000 2.528529000 H -1.568248000 -0.585197000 3.514095000 C -2.550386000 -2.103589000 2.325123000 H -3.112309000 -2.524224000 3.152395000 C -2.655238000 -2.639495000 1.046311000 H -3.296493000 -3.489898000 0.843960000 C -1.911173000 -2.084051000 0.014417000 H -1.942451000 -2.495957000 -0.991096000 C 1.937806000 -0.662174000 1.137242000 56 H 2.885813000 -0.242934000 1.492644000 H 1.446266000 -1.087231000 2.020579000 C 2.173213000 -1.760876000 0.143953000 C 3.159348000 -2.719179000 0.340171000 H 3.815093000 -2.650694000 1.202782000 C 3.288009000 -3.757822000 -0.573906000 H 4.049320000 -4.518602000 -0.439266000 C 2.424990000 -3.797656000 -1.663902000 H 2.487980000 -4.585723000 -2.405351000 C 1.473819000 -2.799886000 -1.805132000 H 0.802361000 -2.791063000 -2.656830000 C 1.869207000 1.618894000 0.200815000 H 2.635204000 1.855601000 0.949262000 H 1.200620000 2.481975000 0.142031000 C 2.458599000 1.395234000 -1.162517000 C 3.662828000 1.940577000 -1.582228000 H 4.265124000 2.521934000 -0.891060000 C 4.079597000 1.729933000 -2.894385000 H 5.017597000 2.146511000 -3.245615000 C 3.279349000 0.969089000 -3.740754000 H 3.570988000 0.774895000 -4.766648000 C 2.094141000 0.441042000 -3.249917000 H 1.439878000 -0.177773000 -3.857699000 O -0.683560000 -0.901695000 -2.752950000 C -4.747640000 -5.564686000 -5.245184000 C -3.829808000 -4.823536000 -4.533300000 C -4.085031000 -3.472983000 -4.230230000 C -5.295974000 -2.877284000 -4.672718000 C -6.218977000 -3.634852000 -5.402455000 C -5.942403000 -4.961028000 -5.679228000 H -4.552729000 -6.606565000 -5.474141000 H -2.893733000 -5.250374000 -4.188342000 C -3.108462000 -2.681450000 -3.498690000 H -7.135770000 -3.161182000 -5.734776000 57 H -6.665012000 -5.543643000 -6.242191000 C -4.828634000 -0.731208000 -3.604889000 C -3.571443000 -1.367802000 -3.231257000 H -1.063218000 -1.833856000 -2.822075000 C -4.632192000 0.597197000 -4.300035000 C -3.715032000 0.701761000 -5.351615000 C -5.392153000 1.706058000 -3.930196000 C -3.574071000 1.903407000 -6.037070000 H -3.140046000 -0.173162000 -5.653084000 C -5.249497000 2.909955000 -4.615978000 H -6.113367000 1.619912000 -3.120500000 C -4.344628000 3.008317000 -5.671367000 H -2.879824000 1.975673000 -6.868842000 H -5.859578000 3.764828000 -4.340492000 H -4.248206000 3.941281000 -6.218531000 O -1.976821000 -3.120717000 -3.152021000 O -5.634310000 -1.587110000 -4.465933000 H -1.422043000 -0.366074000 -3.080209000 H -5.447010000 -0.570206000 -2.705634000 58