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 DEX225 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
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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
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C
-5.196881000
2.898743000
-4.837575000
H
-6.007966000
1.613232000
-3.309924000
C
-4.240993000
3.034099000
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H
-2.606594000
2.096711000
-6.888515000
H
-5.906217000
3.699065000
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H
-4.204208000
3.940974000
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O
-1.832421000
-3.205432000
-3.175719000
O
-5.448823000
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-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