Supporting Information

S1

Supporting Information

A Mononuclear Nonheme High-Spin Iron(III)-Hydroperoxo Complex as an

Active Oxidant in Sulfoxidation Reaction

Yun Mi Kim,

†

_{Kyung-Bin Cho,}

†

_{Jaeheung Cho,}

†,

§

_{Binju Wang,}

‡

_{Chunsen Li,}

‡

_{Sason Shaik*}

,

‡

_and

Wonwoo Nam*

,

†

†

_{Department of Bioinspired Science, Ewha Womans University, Seoul 120-750, Korea.}

‡

_{Institute of Chemistry and the Lise Meitner-Minerva Center for Computational Quantum}

Chemistry, The Hebrew University of Jerusalem, 91904 Jerusalem, Israel.

§

_{Department of Emerging Materials Science, DGIST, Daegu 711-873, Korea.}

Table of Contents

Table of Contents

... 2

Experimental Section

... 5

Materials and Instrumentation

... 5

Reactivity Studies and Product Analysis

... 6

References (Experimental Section)

... 6

Table S1.

... 8

Data for the Reactions of

1

and

para

-X-Ph-SCH

3

in acetone/CF

3

CH

2

OH (3:1) at –20 °C. ... 8

Figure S1.

... 9

UV-vis spectral changes showing the conversion of [(TMC)Fe

III

_(OOH)]

2+

₍

₁

_{) (red) to [(TMC)Fe}

IV

_(O)]

2+

₍

₂

₎

(green) in the reaction of [(TMC)Fe

III

_(OO)]

+

_{(blue) and 10 equiv HClO}

4

in acetone/CF

3

CH

2

OH (3:1) at –20 °C.

... 9

Figure S2.

... 10

Plot of

k

obs

against the concentration of 4-methoxythioanisole to determine a second-order rate constant in the

reaction of [(TMC)Fe

III

_(OOH)]

2+

₍

₁

_{) with}

_{4-methoxythioanisole in acetone/CF}

3

CH

2

OH (3:1) at –20 °C. ... 10

Figure S3.

... 11

Plot of first-order rate constants against 1/T to determine activation parameters in the reaction of

[(TMC)Fe

III

_(OOH)]

2+

₍

₁

_{) (1 mM) with}

_{100 equiv of}

_{4-methoxythioanisole in acetone/CF}

3

CH

2

OH (3:1). ... 11

Figure S4.

... 12

Plots of

k

obs

against the concentration of substrates to determine a second-order rate constant in the reaction of

[(TMC)Fe

III

_(OOH)]

2+

₍

₁

_{) with (a) 4-methylthioanisole, (b) 4-fluorothioanisole, and (c) thioanisole in}

acetone/CF

3

CH

2

OH (3:1) at –20 °C. ... 12

Figure S5.

... 13

LC-ESI-MS spectra of CH

3

S(O)Ph; (a) standard CH

3

S(

16

O)Ph, (b) CH

3

S(

16

O)Ph obtained in the reaction of

[(TMC)Fe

III

₍

16

_O

16

_OH)]

2+

₍

₁

_-

16

_{O) with thioanisole (CH}

3

SPh), and (c) CH

3

S(

18

O)Ph obtained in the reaction of

[(TMC)Fe

III

₍

18

_O

18

_OH)]

2+

₍

₁

_-

18

_{O) with CH}

3

SPh. ... 13

Figure S6.

... 14

X-band EPR spectrum recorded at 4.3 K, after the completion of the reaction of [(TMC)Fe

III

_(OOH)]

2+

₍

₁

_{) with}

100 equiv of 4-methoxythioanisole in acetone/CF

3

CH

2

OH (3:1) at –20 °C. ... 14

Figure S7.

... 15

ESI-MS spectrum recorded after the completion of the reaction of [(TMC)Fe

III

_(OOH)]

2+

₍

₁

_{) with 100 equiv of}

4-methoxythioanisole in acetone/CF

3

CH

2

OH (3:1) at –20 °C. ... 15

S3

Time courses of the absorbance at 547 nm for [(N4Py)Fe

III

_(OOH)]

2+

₍

₃

_{) in the presence (●),}

_k

obs

= 4.0 × 10

-3

s

-1

,

and absence (

●

) ,

k

obs

= 3.6 × 10

-3

s

-1

, of 100 equiv 4-methoxythioanisole in CH

3

OH at 25 °C. ... 16

Figure S9.

... 17

Plots of

k

obs

against the concentration of 4-methoxythioanisole to determine second-order rate constants in the

reactions of [(TMC)Fe

III

_(OOH)]

2+

₍

₁

_{) (●) and [(TMC)Fe}

IV

_(O)]

2+

₍

₂

_{) (}

_■

_{) with}

_{4-methoxythioanisole in}

acetone/CF

3

CH

2

OH (3:1) at –20 °C. ... 17

Figure S10.

... 18

Plots of

k

obs

against the concentration of 4-methoxythioanisole to determine second-order rate constants in the

reactions of [(TMC)Fe

III

_(OOH)]

2+

₍

₁

_{) (●) and [(TMC)Fe}

IV

_(O)]

2+

₍

₂

_{) (}

_▲

_{) in the presence of 10 equiv HClO}

4

with

4-methoxythioanisole in acetone/CF

3

CH

2

OH (3:1) at –20 °C. ... 18

Figure S11.

... 19

Time courses of the absorbance at 526 nm for the reaction of [(TMC)Fe

III

_(OOH)]

2+

₍

₁

_{) with}

4-methoxythioanisole in the presence of 3 equiv (

■

),

k

obs

= 3.0 × 10

-2

s

-1

, 10 equiv (●) ,

k

obs

= 2.3 × 10

-2

s

-1

and

100 equiv (

▲

),

k

obs

= 2.0 × 10

-2

s

-1

, of HClO

4

in acetone/CF

3

CH

2

OH (3:1) at –20 °C. ... 19

DFT Section

... 20

Methods

... 20

Orbitals of the Sulfoxidation Reaction

... 21

Homolytic Concerted Pathways.

... 22

References (DFT Section)

... 22

Figure S12.

... 25

Reaction energy diagram of thioanisole sulfoxidation reaction by [(N4Py)Fe

III

_OOH]

2+

_{. ... 25}

Table S2.

... 26

Energies for sulfoxidation of thioanisole by [(14-TMC)Fe

III

_OOH]

2+

_{. ... 26}

Table S3.

... 27

Energies for sulfoxidation of thioanisole by [(N4Py)Fe

III

_OOH]

2+

_{. ... 27}

Table S4.

... 28

Energies for sulfoxidation of thioanisole by [(TPA)Fe

III

_OOH(CNCH

3

)]

2+

. ... 28

Table S5.

... 29

Mulliken spin density distribution for [(14-TMC)Fe

III

_OOH]

2+

_{. ... 29}

Table S6.

... 29

Mulliken spin density distribution for [(N4Py)Fe

III

_OOH]

2+

_{. ... 29}

Table S7.

... 30

Mulliken spin density distribution for [(TPA)Fe

III

_OOH(CNCH

3

)]

2+

. ... 30

Table S8.

... 30

Geometries of [(14-TMC)Fe

III

_OOH]

2+

_{in Å and degrees. ... 30}

Geometries of [(N4Py)Fe

III

_OOH]

2+

_{in Å and degrees. ... 31}

Table S10.

... 31

Geometries of [(TPA)Fe

III

_OOH(CNCH

3

)]

2+

in Å and degrees. ... 31

Coordinates

... 32

S5

Experimental Section

Materials and Instrumentation

All chemicals obtained from Aldrich Chemical Co. were the best available purity and used

without further purification unless otherwise indicated. Solvents were dried according to

published procedures and distilled under Ar prior to use.

S1

H

2

18

O

2

(90%

18

O-enriched, 2% H

2

18

O

2

in water) was purchased from ICON Services Inc. (Summit, NJ, USA). [(TMC)Fe

III

(OO)]

+

,

[(TMC)Fe

III

_(OOH)]

2+

₍

₁

_{) and [(TMC)Fe}

IV

_(O)]

2+

₍

₂

_{) were prepared according to the literature}

methods.

S2,S3

[(N4Py)Fe

III

(OOH)]

2+

was prepared by reacting [(N4Py)Fe

II

]

2+

with 10 equiv H

2

O

2

in CH

3

OH.

S4

UV-vis spectra were recorded on a Hewlett Packard 8453 diode array spectrophotometer

equipped with a UNISOKU Scientific Instrument for low-temperature experiments. Electrospray

ionization mass spectra (ESI-MS) were collected on a Thermo Finnigan (San Jose, CA, USA)

LCQ

TM

_{Advantage MAX quadrupole ion trap instrument, by infusing samples directly into the}

source using a manual method. The spray voltage was set at 4.2 kV and the capillary temperature

at 80

C. Electrochemical measurements were performed on a CH Instrument (CHI630B)

electrochemical analyzer in deaerated CH

3

CN in the presence of 0.1 M Bu

4

NPF

6

as a supporting

electrolyte. A conventional three-electrode cell was used with a platinum working electrode

(surface area of 0.3 mm

2

) and a platinum wire as a counter electrode. The platinum working

electrodes (BAS) were routinely polished with BAS polishing alumina suspension and rinsed

with CH

3

CN before use. The measured potentials were recorded as a function of Ag/AgNO

3

(0.01 M) reference electrode. All potentials (vs Ag/Ag

+

_{) were converted to values vs SCE by}

adding 0.29 V.

S4

All electrochemical measurements were performed under Ar atmosphere.

CW-EPR spectra were taken at 4.3 K using an X-band Bruker EMX-plus spectrometer equipped with

a dual mode cavity (ER 4116DM). Low temperatures were achieved and controlled using an

Oxford Instruments ESR900 liquid He quartz cryostat with an Oxford Instruments ITC503

temperature and gas flow controller. LC-ESI-MS spectra were collected on a Finnigan Surveyor

Integrated HPLC systems (PDA detector and LC pump) connected with Thermo Finnigan (San

Jose, CA, USA) LCQ

TM

Advantage MAX quadrupole ion trap instrument. The separation of

products was achieved by on-column injection to a Hypersil GOLD column (5

, 4.6  250 mm)

using a MeOH:H

2

O (3:1) eluent at a flow rate of 1 mL/min, at the spray voltage 4.8 kV and the

capillary temperature at 250 ºC. All products

m/z

are corresponding to [M+1]

+

_.

Reactivity Studies and Product Analysis

All reactions were run by monitoring UV-vis spectral changes of reaction solutions, and rate

constants were determined by fitting the changes in absorbance at 526 nm for

1

and 823 nm for

2

.

Reactions were run at least in triplicate, and the data reported represent the average of these

reactions. After the completion of reactions, pseudo-first-order fitting of the kinetic data allowed

us to determine

k

obs

values. Products formed in the oxidation of thioanisoles by

1

and

2

in

acetone/CF

3

CH

2

OH (3:1) at –20 °C were analyzed by HPLC. Phenyl methyl sulfoxides (>80%)

were formed as a sole product in the oxidation of thioanisoles by

1

and

2

. The

18

O-labeling

experiment for the oxidation of thioanisoles by

1

-

18

O was analyzed by LC-ESI-MS by comparing

the relative abundances of

16

O and

18

O. The

18

O-labeled product was obtained with a quantitative

yield (~90%) (Figure S5).

References (Experimental Section)

S7

S2

Annaraj, J.; Suh, Y.; Seo, M. S.; Kim, S. O.; Nam, W.

Chem. Commun.

2005

, 4529–4531.

S3

Cho, J.; Jeon, S.; Wilson, S. A.; Liu, L. V.; Kang. E. A.; Braymer, J. J.; Lim, M. H.;

Hedman, B.; Hodgson, K. O.; Valentine, J. S.; Solomon, E. I.; Nam, W. Structure and

reactivity of a mononuclear non-haem iron(III)-peroxo complex.

Nature

2011

,

478

, 502–

505.

S4

Mann, C. K.; Barnes, K. K.

Electrochemical Reactions in Non-aqueous Systems

; Mercel

Dekker: New York, 1970.

Table S1.

Data for the Reactions of

1

and

para

-X-Ph-SCH

3

in acetone/CF

3

CH

2

OH (3:1) at –20 °C.

X

σ

p

+

E

ox

(SCE,V)

k

2

(M

–1

s

–1

)

OCH

3

–0.78

0.76

1.8 × 10

–1

CH

3

–0.31

0.95

5.4 × 10

–2

F

–0.07

1.07

3.2 × 10

–3

S9

Figure S1.

UV-vis spectral changes showing the conversion of [(TMC)Fe

III

(OOH)]

2+

(

1

) (red) to

[(TMC)Fe

IV

(O)]

2+

(

2

) (green) in the reaction of [(TMC)Fe

III

(OO)]

+

(blue) and 10 equiv HClO

4

in

acetone/CF

3

CH

2

OH (3:1) at –20 °C.

Inset shows the time course of the absorbance change of

1

at

Figure S2.

Plot of

k

obs

against the concentration of 4-methoxythioanisole to determine a second-order rate

constant in the reaction of [(TMC)Fe

III

(OOH)]

2+

(

1

) with

4-methoxythioanisole in

acetone/CF

3

CH

2

OH (3:1) at –20 °C.

S11

Figure S3.

Plot of first-order rate constants against 1/T to determine activation parameters in the reaction of

[(TMC)Fe

III

(OOH)]

2+

(

1

) (1 mM) with

100 equiv of

4-methoxythioanisole in acetone/CF

3

CH

2

OH

Figure S4.

Plots of

k

obs

against the concentration of substrates to determine a second-order rate constant in

the reaction of [(TMC)Fe

III

(OOH)]

2+

(

1

) with (a) 4-methylthioanisole, (b) 4-fluorothioanisole,

and (c) thioanisole in acetone/CF

3

CH

2

OH (3:1) at –20 °C.

S13

Figure S5.

LC-ESI-MS spectra of CH

3

S(O)Ph; (a) standard CH

3

S(

16

O)Ph, (b) CH

3

S(

16

O)Ph obtained in the

reaction of [(TMC)Fe

III

(

16

O

16

OH)]

2+

(

1

-

16

O) with thioanisole (CH

3

SPh), and (c) CH

3

S(

18

O)Ph

Figure S6.

X-band EPR spectrum recorded at 4.3 K, after the completion of the reaction of

[(TMC)Fe

III

(OOH)]

2+

(

1

) with 100 equiv of 4-methoxythioanisole in acetone/CF

3

CH

2

OH (3:1) at

–20 °C. Instrumental parameters: microwave power = 1.0 mW, microwave frequency = 9.647

GHz, modulation amplitude = 0.10 mT receive gain 1.0 × 10

4

_{and modulation frequency = 100}

S15

Figure S7.

ESI-MS spectrum recorded after the completion of the reaction of [(TMC)Fe

III

(OOH)]

2+

(

1

) with

100 equiv of 4-methoxythioanisole in acetone/CF

3

CH

2

OH (3:1) at –20 °C. Peaks were assigned

as follows:

m/z

461.2 (major, relative intensity 100%) for [(TMC)Fe

II

_(CF

3

SO

3

)]

+

,

m/z

176.6 for

[(TMC)Fe

II

_(CH

3

CN)]

2+

,

m/z

156.2 for [(TMC)Fe

II

]

2+

and

m/z

185.1 (relative intensity

ca

. 10%)

for [(TMC)Fe

III

_(OH)(CH

Figure S8.

Time courses of the absorbance at 547 nm for [(N4Py)Fe

III

(OOH)]

2+

(

3

) in the presence (

●

),

k

obs

= 4.0 × 10

-3

s

-1

, and absence (●) ,

k

obs

= 3.6 × 10

-3

s

-1

, of 100 equiv 4-methoxythioanisole in

S17

Figure S9.

Plots of

k

obs

against the concentration of 4-methoxythioanisole to determine second-order rate

constants in the reactions of [(TMC)Fe

III

(OOH)]

2+

(

1

) (

●

) and [(TMC)Fe

IV

(O)]

2+

(

2

) (■) with

4-methoxythioanisole in acetone/CF

3

CH

2

OH (3:1) at –20 °C.

Figure S10.

Plots of

k

obs

against the concentration of 4-methoxythioanisole to determine second-order rate

constants in the reactions of [(TMC)Fe

III

(OOH)]

2+

(

1

) (

●

) and [(TMC)Fe

IV

(O)]

2+

(

2

) (▲) in the

S19

Figure S11.

Time courses of the absorbance at 526 nm for the reaction of [(TMC)Fe

III

(OOH)]

2+

(

1

) with

4-methoxythioanisole in the presence of 3 equiv (■),

k

obs

= 3.0 × 10

-2

s

-1

, 10 equiv (

●

) ,

k

obs

= 2.3 ×

10

-2

_s

-1

_{and 100 equiv (▲),}

_k

DFT Section

Methods

Density functional theory (DFT)

S5

was applied at the B3LYP/LACV3P

*+

//B3LYP/LACVP

level

S6

(6-311+G(3df)//6-311+G*on S) using Gaussian 09.

S7

In previous trials, in C-H activation

reactions, we have found that using gas-phase optimizations for highly charged species such as

the current system (2+) can cause a hydride transfer (i.e. one proton and two electrons) rather

than a net hydrogen atom transfer from the substrate to the Fe

IV

O due to self-interaction errors

(SIE). While sulfoxidation reactions are untested in this aspect, performing the optimizations in

solvent avoids these artificial results for the H-abstraction step;

S8

hence, the solvent effects were

included using CPCM model with UFF cavity,

S9

per G09 default. The solvent used in the

calculations was 2,2,2-trifluoroethanol. There were some trial calculations done in acetonitrile as

well, and the differences due to this change in the dielectric media were found to be small, hence

the conclusion was drawn that the effect of the exact solvent type on the obtained energies was

minimal. However, using solvent effects during the optimization may give rise to other problems.

Adding thermal contributions then becomes in principle inaccurate since the standard solvent

models are parameterized to yield good solvation free energies and not any other property. This

means that thermal effects are already included, to a certain extent, in the obtained electronic

energies, hence possibly double counting the thermal contributions

S10

(the same consideration

applies to the dispersion correction as well). On the other hand, gas-phase frequency calculations

on the so obtained structure may not be meaningful either since the structure may not be in a

stationary point without the solvent. This leaves us in principle with no easily available options to

calculate in a uniform manner the free energies and at the same time avoid SIE, for highly charge

S21

be more time consuming and sometimes leading to ‘reactions’ between the transition metal

complex and the counter ions, which may or may not be realistic.

Therefore, we use throughout this study the electronic energy barriers (Δ

E

‡

) without any

correction factors (except for solvent modelling, which is included by default on all calculations)

due to its simplicity, both in calculation and analysis. Despite the potential errors of this approach,

our experiences are good. For C-H activations in particular, we have shown that this approach

still gives a good numerical agreement to experiments at energy barriers above 12 kcal/mol or

so.

S11

_{We do however also calculate the free energy barriers, Δ}

_G

‡

_{, despite the apparent flaws in}

the approach and provide them in the SI. In doing these calculations, one has to decide what

terms to include in Δ

G

‡

. Conventional calculations usually include Δ

E

‡

, zero-point vibrational

energy (Δ

Z

0

‡

), enthalpy (Δ

E

thermal

‡

) and entropy (-

T

Δ

S

‡

) corrections. We have here also added

dispersion effects, using the DFT-D3 program.

S12

Orbitals of the Sulfoxidation Reaction

The description in the main text regarding orbital mixing in the sulfoxidation reaction is a

somewhat simplified view. One aspect of this is that as the O-O bond break is not fully

implemented before the O-S bond is formed, the orbitals are not as localized as in the description

above. The actual key orbital at the TS can therefore involve all the fragment orbitals at the same

time, i.e. a delocalized combined

d

xz

-

x

-

*

lp

“super-orbital” facilitating all the electron transfers

needed in one single moment within the reaction. Also, the proximal oxygen

p

x

orbital does not

necessarily need to interact with

d

xz

orbital; it can choose to interact with

d

z2

instead, or even to a

certain degree with both. This is possible because the Fe-O-OH angle is significantly larger than

the ideal 90 for the

p

x

-

d

xz

interaction, and more close to 180 for the ideal

p

x

-

d

z2

interaction

actual case we see with the high-spin TMC (but not in the intermediate-spin case, or with N4Py

and TPA ligands). This however is still within our conclusion that the occupation number of the

d

xz

orbital determines the heterolytic or hemolytic cleavage, as the occupation number on

d

xz

and

d

z2

is the same in high-spin

1

.

Homolytic Concerted Pathways.

The

S

= 3/2 state of

3

was found to have a reactant configuration of (

d

xy

1

,

d

xz

2

,

d

yz

1

,

d

x

2

-y

2

1

,

d

z

2

0

).

According to the pathway selection rule then, this species with doubly occupied

d

xz

orbital would

then choose the homolytic pathway. Surprisingly, only a single concerted TS step in the reaction

for this species was found, without a distinct intermediate. However, a closer look at the spin

density distribution reveals that at the TS, the spin on the leaving OH group is –0.26 (SI, Table

S6). This is closer to the corresponding spin in the homolytic O-O bond breaking TS for low-spin

TMC and N4Py (–0.21 and –0.33, respectively) rather than the corresponding spins from their

high-spin heterolytic reactions (0.06 and 0.05, respectively). Hence, this reaction starts with a

homolytic O-O bond cleavage, and then utilizes the delocalized orbitals at TS for a fast electron

back-transfer together with a proton, resulting in a concerted TS. Hence, this would be an

example of a

homolytic, concerted

reaction. Such a homolytic concerted reaction was found to

occur with

S

= 1/2 [(TPA)Fe

III

_OOH]

2+

_{as well. However,}

_S

_{= 3/2 [(TPA)Fe}

III

_OOH]

2+

_{showed a}

hemolytic, stepwise pathway. This latter case still followed the pathway selection rule as its

valence electron configuration was the same as in

S

= 3/2 [(N4Py)Fe

III

_OOH]

2+

_.

References (DFT Section)

S23

S6

(a) Becke, A. D.

Phys. Rev. A

1988

,

38

, 3098. (b) Becke, A. D.

J. Chem. Phys.

1993

,

98

,

1372-1377. (c) Becke, A. D.

J. Chem. Phys.

1993

,

98

, 5648-5652. (d) Lee, C.; Yang, W.;

Parr, R. G.

Phys. Rev. B

1988

,

37

, 785-789. (e) The LACVP and LACV3P

*+

basis sets uses

pople style 6-31G and 6-311+G* basis sets (respectively) on all atoms except transition

metals, where an ECP is used as defined in the quantum chemistry program Jaguar, version

7.7, Schrödinger, LLC, NewYork, NY, 2010. See also (f) Hay, P. J.; Wadt, W. R.

J. Chem.

Phys

.

1985

,

82

, 299-310. (g) Dyall, K. G.

Theor. Chem. Acc

.

2004

,

112

, 403-409.

S7 Frisch, M. J.; Trucks, G. W.; Schlegel, H. B.; Scuseria, G. E.; Robb, M. A.; Cheeseman, J.

R.; Scalmani, G.; Barone, V.; Mennucci, B.; Petersson, G. A.; Nakatsuji, H; Caricato,

M.; Li, X.; Hratchian, H. P.; Izmaylov, A. F.; Bloino, J.; Zheng, G.; Sonnenberg, J. L.;

Hada, M.; Ehara, M.; Toyota, K.; Fukuda, R.; Hasegawa, J.; Ishida, M.; Nakajima, T.;

Honda, Y.; Kitao, O.; Nakai, H.; Vreven, T.; Montgomery, J. A.; Peralta, J. E.; Ogliaro, F.;

Bearpark, M.; Heyd, J. J.; Brothers, E.; Kudin, K. N.; Staroverov, V. N.; Kobayashi, R.;

Normand, J.; Raghavachari, K.; Rendell, A.; Burant, J. C.; Iyengar, S. S.; Tomasi, J.; Cossi,

M.; Rega, N.; Millam, J. M.; Klene, M.; Knox, J. E.; Cross, J. B.; Bakken, V.; Adamo, C.;

Jaramillo, J.; Gomperts, R.; Stratmann, R. E.; Yazyev, O.; Austin, A. J.; Cammi, R.;

Pomelli, C.; Ochterski, J. W.; Martin, R. L.; Morokuma, K.; Zakrzewski, V. G.; Voth, G. A.;

Salvador, P.; Dannenberg, J. J.; Dapprich, S.; Daniels, A. D.; Farkas, Ö .; Foresman, J. B.;

Ortiz, J. V.; Cioslowski, J.; Fox, D. J.

Gaussian 09, Revision B.01

, Gaussian Inc.:

Wallingford CT,

2009

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J. Chem. Phys.

2008

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154301-13. b) Janardanan, D.; Usharani, D.; Chen, H.; Shaik, S.

J. Phys. Chem. Lett.

2011

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S9

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, 1995. (b) Cossi, M.; Rega, N.;

Scalmani, G.; Barone, V.

J. Comp. Chem

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2003

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S10 Ho, J.; Klamt, A.; Coote, M. L.

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Chem. Eur. J.

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2012

,

18

,

10444-10453.

S25

Figure S12.

Table S2.

Energies for sulfoxidation of thioanisole by [(14-TMC)Fe

III

_OOH]

2+

_.

lacvp

lacv3p

*+



_E

a

Z

0

E

thermal

b

-TS

b

Disp



G

c

S=1/2

Reactant

8.67

+6.35

15.02

+2.13

-0.59

+2.65

-4.44

14.77

TS1

22.71

+9.01

31.72

+0.98

-0.79

+4.40

-5.07

31.23

Intermediate

14.07

+5.85

19.92

+1.59

-0.52

+3.16

-4.22

19.93

TS2

16.93

+6.44

23.37

+0.94

-0.96

+3.93

-4.55

22.73

Product

-29.18

-3.26

-32.43

+2.79

-1.11

+4.91

-5.96

-31.81

S=3/2

Reactant

3.63

+5.35

8.97

+1.10

-0.18

+1.58

-3.41

8.06

TS

17.77

+7.73

25.50

+0.32

-0.52

+2.88

-3.97

24.21

Product

-37.52

-4.31

-41.83

+1.49

-0.67

+2.91

-5.18

-43.28

S=5/2

Reactant

0.00

+0.00

0.00

+0.00

+0.00

+0.00 +0.00

0.00

TS

10.18

+4.32

14.49

-0.81

-0.21

+1.93

-1.45

13.96

Product

-44.16

-6.94

-51.10

+0.28

-0.51

+2.36

-1.54

-50.51

a

_{Sum of the two previous columns.}

b

_{T = 298.15 K.}

c

G = E + Z

0

+ E

thermal

- TS + Disp.

This value is however not deemed to be reliable due to double counting of effects (marked in red)

described in methods section.

S27

Table S3.

Energies for sulfoxidation of thioanisole by [(N4Py)Fe

III

_OOH]

2+

_.

lacvp

lacv3p

*+



_E

a

Z

0

E

thermal

b

-TS

b

Disp



G

c

S=1/2

Reactant

0.00

+0.00

0.00

+0.00

+0.00

+0.00 +0.00

0.00

TS1

18.09

+2.20

20.29

-1.58

-0.10

+2.05

-3.85

16.81

Intermediate

12.51

-0.24

12.28

-1.04

+0.19

+0.43

-2.30

9.56

TS2

14.68

+0.13

14.81

-1.55

-0.28

+1.72

-1.70

13.00

Product

-34.11

-10.30

-44.41

+0.41

-0.37

+1.73

-2.19

-44.82

S=3/2

Reactant

13.53

-4.21

9.32

-1.53

0.61

-1.96

+1.53

7.97

TS

31.85

-2.58

29.26

-2.83

+0.52

-1.03

-0.62

25.30

Product

-21.16

-13.21

-34.37

-1.53

+0.31

-1.36

+0.30

-36.64

S=5/2

Reactant

12.50

-8.68

3.81

-2.25

+1.06

-3.74

+0.84

-0.29

TS

25.22

-5.61

19.61

-3.14

+0.72

-1.85

-1.29

14.05

Product

-30.17

-16.89

-47.06

-2.04

+0.56

-3.34

+0.31

-51.57

a

_{Sum of the two previous columns.}

b

_{T = 298.15 K.}

c

G = E + Z

0

+ E

thermal

- TS + Disp.

This value is however not deemed to be reliable due to double counting of effects (marked in red)

described in methods section.

Table S4.

Energies for sulfoxidation of thioanisole by [(TPA)Fe

III

_OOH(CNCH

3

)]

2+

.

lacvp

lacv3p

*+



_E

a

Z

0

E

thermal

b

-TS

b

Disp



G

c

S=1/2

Reactant

0.00

+0.00

0.00

+0.00

+0.00

+0.00 +0.00

0.00

TS

19.00

+2.67

21.67

-1.38

-0.15

+1.60

-1.34

20.39

Product

-36.56

-8.84

-45.40

+0.51

-0.42

+1.02

-0.03

-44.32

S=3/2

Reactant

11.46

-1.58

9.88

-1.57

+0.73

-3.16

+3.26

9.16

TS

29.40

+0.41

29.81

-2.68

+0.57

-1.07

+0.98

27.60

Intermediate

25.37

-3.50

21.87

-2.59

+1.03

-4.60

+3.56

19.28

S=5/2

Reactant

10.83

-6.64

4.19

-2.58

+1.21

-5.36

+4.03

1.49

TS

23.34

-3.17

20.17

-3.06

+0.75

-1.95

+0.74

16.65

Product

-31.76

-13.96

-45.72

-1.88

+0.56

-2.64

+0.70

-48.98

a

_{Sum of the two previous columns.}

b

_{T = 298.15 K.}

c

G = E + Z

0

+ E

thermal

- TS + Disp.

This value is however not deemed to be reliable due to double counting of effects (marked in red)

described in methods section.

S29

Table S5.

Mulliken spin density distribution for [(14-TMC)Fe

III

_OOH]

2+

_.

Fe

O

proximal

HO

distal

4 x N

S

Substrate excl. S Rest

S=1/2

Reactant

1.02

0.07

0.01

-0.11 0.00

0.00

0.01

TS1

0.95

0.60

-0.21

-0.05 -0.26

-0.02

-0.01

Intermediate 1.37

0.71

-0.48

-0.08 -0.45

-0.03

-0.04

TS2

1.25

0.70

-0.33

-0.06 -0.42

-0.09

-0.03

Product

1.04

0.06

0.00

-0.11 0.00

0.00

0.01

S=3/2

Reactant

3.00

0.28

0.06

-0.36 0.00

0.00

0.02

TS

2.64

0.28

0.07

-0.23 0.20

0.03

0.01

Product

2.97

0.36

0.01

-0.33 0.00

0.00

-0.01

S=5/2

Reactant

4.18

0.38

0.10

0.24

0.01

0.00

0.10

TS

3.98

0.40

0.06

0.28

0.18

0.02

0.08

Product

4.11

0.49

0.01

0.31

0.00

0.00

0.09

Table S6.

Mulliken spin density distribution for [(N4Py)Fe

III

OOH]

2+

.

Fe

O

proximal

HO

distal

5 x N

S

Substrate excl. S Rest

S=1/2

Reactant

0.91

0.19

0.01

-0.13 0.00

0.00

0.01

TS1

0.97

0.78

-0.33

-0.08 -0.29

-0.01

-0.04

Intermediate 1.23

0.86

-0.50

-0.09 -0.45

-0.02

-0.03

TS2

1.08

0.83

-0.32

-0.06 -0.43

-0.06

-0.04

Product

0.95

0.19

-0.01

-0.15 0.00

0.00

0.02

S=3/2

Reactant

3.03

0.03

-0.04

-0.12 0.00

0.00

0.10

TS

2.86

0.62

-0.26

0.01

-0.30

-0.02

0.09

Product

2.77

0.30

0.00

-0.11 0.00

0.00

0.04

S=5/2

Reactant

4.09

0.37

0.07

0.30

0.00

0.00

0.16

TS

3.94

0.43

0.05

0.22

0.20

0.02

0.15

Table S7.

Mulliken spin density distribution for [(TPA)Fe

III

_OOH(CNCH

3

)]

2+

.

Fe

O

proximal

HO

distal

4 x N

S

Substrate excl. S CNCH

3

Rest

S=1/2

Reactant

0.88

0.20

0.02

-0.10 0.00

0.00

-0.01

0.00

TS

0.90

0.80

-0.21

-0.14 -0.32

-0.04

0.03

-0.03

Product

0.91

0.19

-0.01

-0.08 0.00

0.00

-0.01

0.00

S=3/2

Reactant

3.08

0.01

-0.04

-0.24 0.00

0.00

0.10

0.09

TS

2.84

0.61

-0.24

-0.08 -0.30

-0.02

0.10

0.08

Intermediate 3.08

0.73

-0.49

-0.01 -0.45

-0.03

0.10

0.06

S=5/2

Reactant

4.08

0.40

0.10

0.25

0.00

-0.00

0.06

0.11

TS

3.91

0.43

0.06

0.19

0.19

0.02

0.09

0.11

Product

3.97

0.47

0.01

0.32

0.00

-0.00

0.10

0.13

Table S8.

Geometries of [(14-TMC)Fe

III

OOH]

2+

in Å and degrees.

Fe-O

proximal

O

proximal

-O

distal

O

distal

-S H-O

distal

H-O

proximal

Fe-O-O

S=1/2

Reactant

1.78

1.50

3.19

1.01

1.96

118.05

TS1

1.71

1.87

2.40

0.99

2.04

131.74

Intermediate

1.62

2.97

2.32

0.99

2.14

122.54

TS2

1.65

2.68

2.07

1.00

1.79

127.70

Product

1.78

2.73

1.57

1.73

1.00

120.99

S=3/2

Reactant

1.88

1.50

3.20

1.01

1.95

118.33

TS

1.76

1.82

2.27

0.99

1.99

140.39

Product

1.81

2.67

1.57

1.67

1.00

123.05

S=5/2

Reactant

1.88

1.47

3.15

1.02

1.95

120.35

TS

1.77

1.72

2.35

0.99

2.00

148.24

S31

Table S9.

Geometries of [(N4Py)Fe

III

_OOH]

2+

_{in Å and degrees.}

Fe-O

proximal

O

proximal

-O

distal

O

distal

-S H-O

distal

H-O

proximal

Fe-O-O

S=1/2

Reactant

1.81

1.50

3.22

1.00

1.96

117.34

TS1

1.73

2.01

2.39

0.98

2.07

123.24

Intermediate

1.66

2.83

2.32

0.99

1.97

122.63

TS2

1.69

2.61

2.07

1.00

1.71

125.36

Intermediate

1.81

2.75

1.56

1.76

1.00

119.32

S=3/2

Reactant

1.83

1.49

3.21

1.01

1.97

117.48

TS

1.72

1.99

2.31

0.99

2.07

118.66

Product

1.76

2.62

1.57

1.61

1.01

124.38

S=5/2

Reactant

1.88

1.47

3.16

1.01

1.95

120.82

TS

1.77

1.80

2.24

0.99

2.01

144.60

Product

1.77

2.60

1.56

1.59

1.01

164.36

Table S10.

Geometries of [(TPA)Fe

III

OOH(CNCH

3

)]

2+

in Å and degrees.

Fe-O

proximal

O

proximal

-O

distal

O

distal

-S H-O

distal

H-O

proximal

Fe-O-O

S=1/2

Reactant

1.81

1.50

3.24

1.00

1.95

115.86

TS

1.74

2.08

2.18

0.98

2.04

121.38

Product

1.81

2.76

1.56

1.77

1.00

121.14

S=3/2

Reactant

1.84

1.49

3.20

1.01

1.96

120.10

TS

1.74

1.97

2.33

0.98

2.03

124.66

Product

1.66

2.80

2.31

0.99

1.94

128.51

S=5/2

Reactant

1.90

1.46

3.14

1.02

1.95

125.19

TS

1.78

1.79

2.26

0.99

2.01

146.87

Coordinates

The coordinates are given in xyz-format, with (charge/multiplicity) in the comment field.

RC=Reactant Complex, TS=Transition state, I=Intermediate Complex, PC=Product Complex.

70

[(TMC)FeOOH](2/2) RC Fe -0.00195 -0.33115 -0.04562 N -0.33777 -0.26875 2.05755 N 0.39007 -0.38929 -2.11068 N 0.03605 1.76237 0.05952 N 0.80558 -2.26978 0.01917 C 1.86348 -2.33741 1.11660 H 2.34304 -3.32153 1.03773 H 2.61831 -1.58196 0.87376 C 1.59896 0.47686 -2.42446 H 1.83879 0.32915 -3.48473 H 2.44631 0.10940 -1.83925 C 1.26566 2.30418 -0.65940 H 2.13743 1.90831 -0.12830 H 1.26365 3.39350 -0.52513 C 1.53670 -2.43046 -1.30170 H 2.50152 -1.92652 -1.21690 H 1.73630 -3.49239 -1.48401 C -0.66001 1.18062 2.35749 H -0.52490 1.37432 3.42813 H -1.71511 1.33234 2.12393 C 1.36402 -2.11560 2.54051 H 2.21670 -2.30995 3.20275 H 0.60583 -2.85174 2.82218 C 0.21548 2.08694 1.53087 H -0.03053 3.14016 1.70686 H 1.26991 1.94932 1.77830 C 0.70387 -1.84178 -2.41208 H -0.25066 -2.36058 -2.50320 H 1.22464 -1.91232 -3.37424 C -1.51823 -1.07201 2.54396 H -1.68239 -0.85176 3.60514 H -1.33837 -2.13603 2.43502 H -2.39549 -0.80051 1.96319 C 0.90275 -0.68744 2.82732 H 0.68237 -0.57288 3.89630 H 1.70626 0.01148 2.57808 C -1.21475 2.43580 -0.43516 H -2.07591 2.05977 0.11380 H -1.36906 2.23098 -1.48928 H -1.12453 3.51812 -0.29002 C -0.18410 -3.39348 0.16374 H -0.88403 -3.36968 -0.66700 H -0.75221 -3.28717 1.08180 H 0.35400 -4.34798 0.18237 C -0.73642 0.00242 -3.03594 H -1.04470 1.02871 -2.87198 H -1.57766 -0.65882 -2.85927 H -0.39198 -0.10099 -4.07151 C 1.38630 1.96309 -2.14074 H 0.55557 2.37264 -2.72175 H 2.27968 2.48521 -2.50492 O -1.77250 -0.48510 -0.19099 O -2.31707 -1.60217 -1.03308 H -3.17328 -1.17881 -1.36636 S -5.07156 -0.27600 -1.95598 C -5.86092 -1.59091 -2.98034 H -6.91459 -1.35615 -3.14191 H -5.33820 -1.59790 -3.94027 H -5.75908 -2.56591 -2.50057 C -5.98640 -0.41763 -0.40784 C -7.09648 0.41262 -0.17946 C -7.79924 0.32058 1.02837 C -7.39701 -0.59580 2.00829 C -6.28744 -1.42093 1.78239 C -5.57842 -1.33247 0.57855 H -7.40509 1.12311 -0.93905 H -8.65628 0.96291 1.20158 H -7.94299 -0.66491 2.94328 H -5.97156 -2.12945 2.54099 H -4.71275 -1.96322 0.40696 70

[(TMC)FeOOH](2/2) TS1 Fe 0.01106 0.01277 0.02038 N 0.02093 0.06801 2.15117 N 0.09896 -0.01848 -2.07837 N 0.24780 2.10501 0.11898 N 0.72385 -1.95089 -0.06261

C 1.29452 0.77130 -2.57791 H 1.34997 0.62727 -3.66490 H 2.19876 0.33835 -2.14142 C 1.38131 2.58436 -0.77438 H 2.29637 2.11907 -0.39397 H 1.47511 3.66878 -0.63018 C 1.23090 -2.13613 -1.47809 H 2.22653 -1.69239 -1.54112 H 1.33387 -3.20552 -1.69545 C -0.13408 1.53365 2.49652 H 0.17893 1.70337 3.53382 H -1.19639 1.77408 2.42715 C 1.64673 -1.89689 2.34889 H 2.57151 -2.16097 2.87676 H 0.88807 -2.58438 2.73412 C 0.67811 2.37743 1.54620 H 0.55835 3.44389 1.76991 H 1.74189 2.14482 1.62490 C 0.27203 -1.47877 -2.43935 H -0.71458 -1.94065 -2.38613 H 0.63027 -1.56292 -3.47247 C -1.12629 -0.65001 2.81406 H -1.12431 -0.41481 3.88509 H -1.03452 -1.72467 2.69462 H -2.05508 -0.32431 2.35264 C 1.33265 -0.44612 2.71222 H 1.29382 -0.33454 3.80365 H 2.13309 0.20034 2.34200 C -1.01664 2.87114 -0.16189 H -1.81965 2.49930 0.47139 H -1.31687 2.74410 -1.19693 H -0.84860 3.93689 0.03201 C -0.33775 -2.97912 0.21205 H -1.18541 -2.80889 -0.44701 H -0.68840 -2.89610 1.23515 H 0.07554 -3.98230 0.05408 C -1.14243 0.45119 -2.79411 H -1.32622 1.50361 -2.60888 H -1.98650 -0.13214 -2.43690 H -1.00517 0.30429 -3.87248 C 1.24025 2.26405 -2.25740 H 0.35860 2.74066 -2.69481 H 2.09902 2.72727 -2.75901 O -1.69331 -0.13435 0.11104 O -2.90392 -1.21993 -0.82230 H -3.50395 -0.43867 -0.77649 S -4.72000 -2.42981 -1.82992 C -3.71449 -3.94211 -1.95636 H -4.35494 -4.80219 -2.16126 H -3.03674 -3.78403 -2.79710 H -3.13123 -4.10469 -1.04961 C -5.84987 -2.75848 -0.49093 C -6.92936 -1.86127 -0.35711 C -7.84799 -2.02766 0.68178 C -7.70365 -3.08599 1.58962 C -6.63169 -3.97661 1.45405 C -5.69956 -3.81693 0.42200 H -7.05056 -1.04550 -1.06313 H -8.67745 -1.33534 0.77785 H -8.42045 -3.21537 2.39315 H -6.51470 -4.79816 2.15280 H -4.87421 -4.51295 0.33861 70

[(TMC)FeOOH](2/2) IC Fe 0.17198 0.10048 0.12786 N 0.26219 0.37265 2.23427 N 0.12976 -0.17250 -1.95676 N 0.94916 2.03894 -0.00989 N 0.27032 -1.96849 0.26700 C 1.40196 -2.38239 1.19952 H 1.47724 -3.47537 1.13853 H 2.32465 -1.96403 0.78328 C 1.45718 0.21704 -2.58166 H 1.40229 -0.04127 -3.64646 H 2.23985 -0.39926 -2.13032 C 2.11439 2.11022 -0.98815 H 2.89964 1.46301 -0.58543 H 2.48946 3.14125 -0.96611 C 0.65107 -2.44385 -1.12587

H 0.95486 2.01666 3.42722 H -0.39886 2.38160 2.35662 C 1.25474 -1.94935 2.65270 H 2.08257 -2.41366 3.20254 H 0.34524 -2.35299 3.10633 C 1.51856 2.32169 1.36855 H 1.71441 3.39498 1.46804 H 2.47633 1.80384 1.44829 C -0.12497 -1.65669 -2.14986 H -1.20113 -1.81221 -2.04153 H 0.16315 -1.94505 -3.16731 C -1.03873 0.09801 2.94736 H -0.95727 0.45432 3.98024 H -1.26019 -0.96378 2.96503 H -1.84191 0.62055 2.43201 C 1.37808 -0.44271 2.86636 H 1.38044 -0.21553 3.93981 H 2.32618 -0.09210 2.44981 C -0.08512 3.08623 -0.33298 H -0.93493 2.98831 0.33883 H -0.43832 2.96932 -1.35185 H 0.36468 4.07919 -0.22643 C -1.02450 -2.62981 0.66637 H -1.81329 -2.37851 -0.04403 H -1.33262 -2.29399 1.65048 H -0.87453 -3.71520 0.69000 C -0.99618 0.54371 -2.66423 H -0.93943 1.61515 -2.51385 H -1.94382 0.16942 -2.28240 H -0.92184 0.33154 -3.73737 C 1.80703 1.69537 -2.42270 H 1.05223 2.33981 -2.88206 H 2.72486 1.86853 -2.99785 O -1.42209 0.38815 0.14938 O -3.37724 -1.35547 -1.24285 H -3.13817 -0.62842 -0.61689 S -5.52374 -0.65846 -1.77886 C -5.42434 -1.83271 -3.16404 H -6.41919 -2.02118 -3.57163 H -4.80125 -1.35219 -3.91977 H -4.94630 -2.75925 -2.84526 C -6.65090 -1.41933 -0.63514 C -7.12451 -0.59844 0.41050 C -7.99407 -1.12316 1.36884 C -8.39996 -2.46337 1.29681 C -7.92694 -3.27792 0.26044 C -7.05036 -2.76660 -0.70314 H -6.81941 0.44208 0.46537 H -8.35765 -0.48520 2.16733 H -9.07805 -2.86739 2.04063 H -8.23648 -4.31594 0.19950 H -6.69075 -3.41479 -1.49255 70

[(TMC)FeOOH](2/2) TS2 Fe 0.10085 0.06396 0.08241 N 0.11252 0.33838 2.18722 N 0.14827 -0.20718 -2.00350 N 0.86759 2.01253 -0.02727 N 0.21852 -2.00859 0.22261 C 1.32031 -2.40918 1.19341 H 1.40937 -3.50217 1.14464 H 2.25278 -1.98534 0.80508 C 1.50485 0.17985 -2.56162 H 1.50977 -0.08589 -3.62666 H 2.26572 -0.42890 -2.06483 C 2.07620 2.08857 -0.94974 H 2.84614 1.44941 -0.50606 H 2.44462 3.12218 -0.91836 C 0.65099 -2.47657 -1.15483 H 1.73042 -2.33204 -1.23703 H 0.45340 -3.54967 -1.25343 C 0.36622 1.81825 2.38487 H 0.72167 1.99752 3.40638 H -0.59026 2.33121 2.27361 C 1.12568 -1.96685 2.63954 H 1.94251 -2.41805 3.21635 H 0.20805 -2.37851 3.06919 C 1.36858 2.31044 1.37247 H 1.53864 3.38771 1.48045

H 0.22597 -1.98089 -3.21235 C -1.20258 0.04047 2.86199 H -1.15605 0.38481 3.90162 H -1.41287 -1.02363 2.85869 H -1.99531 0.55832 2.32664 C 1.22216 -0.45707 2.84969 H 1.19830 -0.22725 3.92285 H 2.17581 -0.09617 2.45464 C -0.15942 3.04712 -0.40395 H -1.03291 2.94867 0.23692 H -0.47534 2.91185 -1.43296 H 0.27583 4.04687 -0.29480 C -1.08111 -2.68440 0.57394 H -1.86138 -2.38067 -0.12394 H -1.39344 -2.40409 1.57420 H -0.94166 -3.77112 0.53650 C -0.93445 0.50501 -2.77656 H -0.86060 1.57970 -2.65796 H -1.90297 0.16706 -2.41664 H -0.82526 0.25925 -3.83994 C 1.84489 1.66040 -2.39510 H 1.11504 2.30118 -2.89769 H 2.79170 1.83059 -2.92263 O -1.52870 0.33419 0.05776 O -3.40892 -1.09037 -1.22045 H -3.01622 -0.38793 -0.63262 S -5.35780 -0.54288 -1.63669 C -5.30211 -1.64799 -3.07612 H -6.31397 -1.82124 -3.44586 H -4.71239 -1.13070 -3.83357 H -4.80983 -2.58518 -2.81493 C -6.45057 -1.34786 -0.50487 C -6.97176 -0.53893 0.52943 C -7.82151 -1.09806 1.48493 C -8.15534 -2.45879 1.42320 C -7.63109 -3.26147 0.40081 C -6.77449 -2.71773 -0.56064 H -6.72121 0.51634 0.57313 H -8.22623 -0.47219 2.27271 H -8.81835 -2.88943 2.16545 H -7.88636 -4.31447 0.35109 H -6.37377 -3.35433 -1.33962 70

[(TMC)FeOOH](2/2) PC Fe 0.03912 0.02510 0.08788 N 0.10688 0.29137 2.19746 N 0.02868 -0.24076 -1.99394 N 0.84033 1.98069 -0.02111 N 0.12373 -2.05049 0.20945 C 1.24934 -2.46530 1.14820 H 1.32557 -3.55898 1.09248 H 2.17401 -2.04853 0.73425 C 1.39172 0.13021 -2.55640 H 1.39104 -0.14513 -3.61897 H 2.14655 -0.48349 -2.05619 C 2.02372 2.05151 -0.97234 H 2.80501 1.41464 -0.54547 H 2.39553 3.08464 -0.96283 C 0.50921 -2.52965 -1.17850 H 1.59008 -2.41667 -1.28463 H 0.27784 -3.59610 -1.27595 C 0.37891 1.76720 2.39319 H 0.74757 1.94200 3.41134 H -0.57459 2.28794 2.29138 C 1.10264 -2.02821 2.60168 H 1.92862 -2.49603 3.15175 H 0.19101 -2.43046 3.05262 C 1.37257 2.25418 1.36938 H 1.56424 3.32708 1.48859 H 2.32923 1.73756 1.47164 C -0.23108 -1.71857 -2.21354 H -1.30922 -1.87172 -2.13878 H 0.07975 -2.00130 -3.22650 C -1.18653 0.00577 2.91699 H -1.11922 0.39579 3.93955 H -1.37739 -1.06183 2.97009 H -1.99445 0.48401 2.36959 C 1.22703 -0.52021 2.81975 H 1.24284 -0.29907 3.89514

S33

H -0.45293 2.96159 -1.41496 H 0.22671 4.02184 -0.16926 C -1.17384 -2.70457 0.60473 H -1.94220 -2.48997 -0.13683 H -1.51360 -2.32403 1.56201 H -1.02351 -3.78799 0.67873 C -1.03822 0.50523 -2.75686 H -0.98186 1.57076 -2.56825 H -2.01558 0.14169 -2.45207 H -0.90018 0.32308 -3.82951 C 1.75200 1.60888 -2.40750 H 1.01719 2.25190 -2.90005 H 2.68728 1.76272 -2.96013 O -1.70043 0.39613 0.15823 O -3.51272 -1.10837 -1.21305 H -2.33767 -0.14765 -0.39010 S -4.92192 -0.49955 -1.52256 C -5.42102 -1.27880 -3.09748 H -6.44484 -0.97497 -3.32857 H -4.74044 -0.91463 -3.86971 H -5.35169 -2.36489 -3.00556 C -6.10015 -1.30877 -0.41253 C -7.21783 -0.57480 0.00552 C -8.14454 -1.17958 0.86391 C -7.93858 -2.49266 1.30540 C -6.80520 -3.20880 0.89358 C -5.87627 -2.61866 0.03020 H -7.36457 0.44755 -0.32860 H -9.01616 -0.62368 1.19132 H -8.65565 -2.95568 1.97467 H -6.64532 -4.22272 1.24396 H -4.98958 -3.15840 -0.28406 70

[(TMC)FeOOH](2/4) RC Fe 0.20847 -0.27886 0.01085 N -0.13315 -0.20753 2.10140 N 0.75079 -0.28364 -2.02807 N 0.02438 1.86381 0.08634 N 1.50404 -1.96984 0.18536 C 2.49979 -1.86466 1.32220 H 3.12002 -2.77046 1.30334 H 3.14674 -1.01125 1.09705 C 1.78443 0.78554 -2.33868 H 2.05062 0.66735 -3.39674 H 2.67791 0.57256 -1.74719 C 1.16501 2.57617 -0.60746 H 2.07736 2.32123 -0.05934 H 0.99976 3.65656 -0.50019 C 2.28124 -2.01020 -1.11450 H 3.11165 -1.30732 -1.03038 H 2.70886 -3.00935 -1.25573 C -0.70073 1.17904 2.34468 H -0.66748 1.39857 3.41806 H -1.74964 1.15591 2.04410 C 1.88359 -1.68867 2.70630 H 2.71604 -1.68958 3.42073 H 1.26436 -2.54484 2.98786 C 0.07377 2.21000 1.55886 H -0.34529 3.21059 1.71701 H 1.12119 2.24357 1.86338 C 1.36315 -1.65358 -2.25821 H 0.53902 -2.36360 -2.34320 H 1.90469 -1.65189 -3.21138 C -1.17113 -1.19627 2.56756 H -1.41547 -0.98713 3.61537 H -0.80061 -2.21347 2.49302 H -2.05543 -1.09334 1.94345 C 1.14550 -0.36730 2.90459 H 0.87321 -0.25450 3.96188 H 1.80931 0.46001 2.64358 C -1.30344 2.31357 -0.46982 H -2.11445 1.78023 0.02161 H -1.36223 2.11091 -1.53394 H -1.41353 3.39200 -0.30639 C 0.68876 -3.23584 0.30014 H -0.09889 -3.24753 -0.45083 H 0.22412 -3.30053 1.27883 H 1.34984 -4.10011 0.16972 C -0.42091 -0.16007 -2.97039 H -0.89831 0.80857 -2.86935 H -1.13997 -0.94207 -2.73950 H -0.05615 -0.27053 -3.99825 C 1.33974 2.22403 -2.08205 H 0.45556 2.48593 -2.67005 H 2.14135 2.86775 -2.46447 O -1.60383 -0.68664 -0.30284 O -1.93794 -2.00771 -0.92562 H -2.92545 -1.89079 -1.08909 S -5.09046 -1.63482 -1.31431 C -5.57435 -3.09718 -2.32848 H -6.65838 -3.22339 -2.30939 H -5.24990 -2.89051 -3.35155 H -5.08137 -3.99967 -1.96257 C -5.64355 -2.13160 0.32929

C -6.92760 -1.77094 0.77063 C -7.35343 -2.14121 2.05223 C -6.50174 -2.86730 2.89463 C -5.21931 -3.22268 2.45661 C -4.78651 -2.85462 1.17703 H -7.58474 -1.20618 0.11776 H -8.34579 -1.86179 2.39033 H -6.83426 -3.15182 3.88741 H -4.55608 -3.78207 3.10811 H -3.79043 -3.11931 0.83843 70

[(TMC)FeOOH](2/4) TS Fe 0.06350 0.00912 0.08757 N 0.12611 0.10390 2.19348 N 0.27862 -0.06641 -1.99959 N 0.43110 2.14168 0.16682 N 0.99644 -1.96514 0.06257 C 2.14572 -2.13364 1.02525 H 2.51996 -3.16349 0.93743 H 2.94074 -1.46036 0.68965 C 1.46063 0.75158 -2.49379 H 1.52055 0.59757 -3.57919 H 2.36693 0.33187 -2.05068 C 1.56829 2.59619 -0.71687 H 2.47827 2.12564 -0.33115 H 1.67680 3.68351 -0.59928 C 1.51876 -2.12436 -1.34320 H 2.48932 -1.62799 -1.40144 H 1.68154 -3.18675 -1.56593 C -0.04548 1.57356 2.52108 H 0.22237 1.74616 3.57043 H -1.10519 1.80726 2.40579 C 1.80931 -1.83040 2.48309 H 2.71413 -2.04531 3.06538 H 1.04828 -2.51245 2.87360 C 0.80304 2.42300 1.60251 H 0.66111 3.48818 1.82357 H 1.86554 2.20464 1.72431 C 0.53198 -1.52694 -2.32075 H -0.43018 -2.03905 -2.27279 H 0.90258 -1.61092 -3.34951 C -1.01193 -0.62871 2.85333 H -1.00847 -0.40784 3.92739 H -0.91193 -1.70053 2.71447 H -1.94198 -0.30279 2.39394 C 1.45376 -0.37103 2.76082 H 1.41366 -0.20504 3.84549 H 2.23854 0.27315 2.35704 C -0.82934 2.89695 -0.16279 H -1.63838 2.56954 0.48641 H -1.12876 2.71115 -1.18920 H -0.65485 3.97185 -0.02947 C -0.06846 -2.99767 0.30715 H -0.93299 -2.79399 -0.32198 H -0.39355 -2.97025 1.34250 H 0.32860 -3.99688 0.08832 C -0.97114 0.33462 -2.74083 H -1.18096 1.38979 -2.59676 H -1.80543 -0.24920 -2.35919 H -0.82560 0.14632 -3.81144 C 1.40422 2.24797 -2.19297 H 0.51300 2.71412 -2.62299 H 2.25171 2.70229 -2.72121 O -1.69039 -0.12188 0.07985 O -3.01536 -1.19304 -0.56680 H -3.55149 -0.36609 -0.59153 S -4.75500 -2.42561 -1.34121 C -3.65598 -3.81860 -1.73961 H -4.24412 -4.72778 -1.87698 H -3.16089 -3.55648 -2.67610 H -2.90589 -3.95782 -0.96099 C -5.61627 -2.94051 0.13025 C -6.79020 -2.22594 0.44276 C -7.51011 -2.54571 1.59653 C -7.07119 -3.57608 2.43911 C -5.90470 -4.28496 2.12479 C -5.16933 -3.96957 0.97696 H -7.13871 -1.43519 -0.21404 H -8.41461 -1.99559 1.83210 H -7.63442 -3.82524 3.33177 H -5.56124 -5.08350 2.77357 H -4.26638 -4.52401 0.75367 70

[(TMC)FeOOH](2/4) PC Fe 0.00000 0.00000 0.00000 N 0.00000 0.00000 2.11489 N 0.26836 0.00000 -2.09600 N 0.37538 2.11672 0.16855 N 0.91656 -1.97345 -0.08241 C 2.05398 -2.15500 0.89402 H 2.45964 -3.16734 0.75889 H 2.83372 -1.44146 0.60913 C 1.48030 0.81948 -2.50968

H 1.58666 0.69893 -3.59528 H 2.36164 0.37736 -2.03944 C 1.53142 2.60962 -0.67063 H 2.43491 2.13744 -0.27253 H 1.62380 3.69369 -0.51848 C 1.46470 -2.09450 -1.48464 H 2.44367 -1.61217 -1.50828 H 1.61613 -3.15177 -1.73521 C -0.17371 1.46116 2.48478 H 0.05935 1.59454 3.54783 H -1.22759 1.70592 2.34256 C 1.67793 -1.94349 2.35792 H 2.56880 -2.18471 2.95094 H 0.91346 -2.65461 2.68440 C 0.71180 2.33439 1.62545 H 0.57786 3.39145 1.88560 H 1.76737 2.09521 1.76590 C 0.50400 -1.45416 -2.46076 H -0.46828 -1.95041 -2.44586 H 0.89412 -1.50859 -3.48425 C -1.16850 -0.74495 2.70525 H -1.23415 -0.51435 3.77500 H -1.04001 -1.81652 2.58771 H -2.07091 -0.43629 2.18316 C 1.30192 -0.50612 2.71141 H 1.21090 -0.40789 3.80109 H 2.10051 0.16411 2.38467 C -0.88412 2.87718 -0.15721 H -1.72463 2.45938 0.39279 H -1.10688 2.80958 -1.21751 H -0.74909 3.93276 0.10771 C -0.13696 -3.03072 0.11683 H -0.95005 -2.89605 -0.59510 H -0.55333 -2.97010 1.11727 H 0.31442 -4.02138 -0.02068 C -0.94604 0.46224 -2.86103 H -1.20529 1.48085 -2.59285 H -1.78401 -0.19090 -2.63096 H -0.72449 0.41947 -3.93421 C 1.41644 2.30547 -2.16275 H 0.54151 2.78633 -2.60961 H 2.28247 2.77497 -2.64549 O -1.79085 -0.21031 -0.08608 O -2.96883 -2.01961 -1.64962 H -2.32054 -0.87977 -0.61081 S -4.43351 -2.53725 -1.45538 C -5.17517 -2.45956 -3.12279 H -6.16756 -2.91513 -3.08565 H -5.25827 -1.40457 -3.39169 H -4.53392 -2.98673 -3.83239 C -4.32717 -4.33398 -1.26616 C -5.27172 -4.96510 -0.44640 C -5.20658 -6.35442 -0.28069 C -4.19835 -7.09007 -0.91600 C -3.24842 -6.44250 -1.71941 C -3.30715 -5.05658 -1.89854 H -6.04226 -4.38758 0.05462 H -5.93419 -6.85535 0.34825 H -4.14752 -8.16507 -0.78060 H -2.46448 -7.01474 -2.20353 H -2.56884 -4.54411 -2.50552 70

[(TMC)FeOOH](2/6) RC Fe 0.23777 -0.23790 0.08167 N 0.19376 -0.00363 2.31966 N 0.65593 -0.36611 -2.12130 N 0.14564 1.94439 0.07594 N 1.65776 -1.91977 0.18519 C 2.72254 -1.72040 1.24746 H 3.39665 -2.58667 1.19974 H 3.29687 -0.83565 0.95478 C 1.57027 0.73625 -2.61174 H 1.68340 0.61102 -3.69763 H 2.55277 0.58027 -2.15830 C 1.18411 2.56811 -0.83519 H 2.16435 2.29096 -0.43419 H 1.08322 3.65857 -0.74862 C 2.34011 -1.94824 -1.16463 H 3.11917 -1.18313 -1.15528 H 2.83435 -2.91778 -1.30427 C -0.24551 1.43296 2.49667 H -0.03002 1.76146 3.52152 H -1.32904 1.46227 2.36732 C 2.21496 -1.54710 2.68026 H 3.10054 -1.59631 3.32626 H 1.58855 -2.38862 2.99166 C 0.44749 2.35140 1.50289 H 0.12692 3.38829 1.66172 H 1.53146 2.31954 1.63055 C 1.34970 -1.70053 -2.28844 H 0.57815 -2.47297 -2.30876 H 1.86578 -1.73030 -3.25652 C -0.83202 -0.89815 2.96007 H -0.91214 -0.66785 4.02971

H -0.54933 -1.94329 2.84721 H -1.79477 -0.74329 2.47512 C 1.54232 -0.20399 2.97415 H 1.40534 -0.09027 4.05868 H 2.19922 0.60355 2.63996 C -1.23773 2.40685 -0.30171 H -1.97137 1.99700 0.38981 H -1.49262 2.06651 -1.30234 H -1.27555 3.50219 -0.27186 C 0.91837 -3.21844 0.41096 H 0.17310 -3.36189 -0.37089 H 0.40266 -3.19628 1.36850 H 1.62944 -4.05263 0.40240 C -0.61219 -0.38608 -2.92992 H -1.13843 0.56137 -2.83494 H -1.25812 -1.18399 -2.56636 H -0.37376 -0.55566 -3.98754 C 1.10176 2.16053 -2.30724 H 0.11041 2.35731 -2.72618 H 1.78031 2.83088 -2.84946 O -1.61586 -0.52229 -0.05286 O -2.14518 -1.87490 -0.25396 H -3.13191 -1.68896 -0.41496 S -5.19544 -1.33060 -0.79626 C -5.45434 -2.33292 -2.32259 H -6.52093 -2.41515 -2.53847 H -4.95968 -1.79770 -3.13708 H -5.01272 -3.32459 -2.21055 C -6.01289 -2.34316 0.45232 C -7.40570 -2.25361 0.61734 C -8.04258 -3.02948 1.59268 C -7.29362 -3.88566 2.41081 C -5.90430 -3.96631 2.25367 C -5.26111 -3.19795 1.27571 H -7.98365 -1.58290 -0.00990 H -9.11828 -2.96068 1.71589 H -7.78957 -4.48335 3.16830 H -5.32090 -4.62525 2.88812 H -4.18472 -3.25845 1.15524 70

[(TMC)FeOOH](2/6) TS Fe 0.00305 -0.02084 0.02718 N -0.04264 0.09854 2.27162 N 0.43854 -0.09401 -2.17401 N 0.39678 2.13129 0.14957 N 0.97155 -1.98859 0.04812 C 2.02562 -2.12236 1.12693 H 2.45868 -3.12939 1.04398 H 2.81455 -1.40211 0.88737 C 1.60393 0.77933 -2.57634 H 1.72809 0.69272 -3.66548 H 2.50453 0.36998 -2.11015 C 1.58034 2.55563 -0.69700 H 2.45837 2.04558 -0.28793 H 1.72224 3.63541 -0.54913 C 1.65043 -2.10580 -1.29777 H 2.59690 -1.56401 -1.23591 H 1.88718 -3.15835 -1.50035 C -0.15963 1.58134 2.52951 H 0.09695 1.79823 3.57503 H -1.20728 1.85460 2.38790 C 1.54927 -1.89236 2.56269 H 2.38558 -2.18280 3.21123 H 0.73313 -2.57115 2.82926 C 0.73804 2.38284 1.60106 H 0.64248 3.45400 1.81989 H 1.78633 2.11241 1.74415 C 0.78020 -1.54613 -2.41239 H -0.15979 -2.09650 -2.48781 H 1.29669 -1.65234 -3.37566 C -1.25671 -0.57693 2.84374 H -1.32675 -0.37046 3.91962 H -1.19839 -1.65377 2.69874 H -2.14216 -0.20641 2.33031 C 1.21288 -0.44090 2.91619 H 1.09921 -0.34540 4.00572 H 2.04550 0.20099 2.61515 C -0.83529 2.90744 -0.22567 H -1.65865 2.63667 0.43348 H -1.13116 2.67396 -1.24558 H -0.63573 3.98310 -0.14222 C -0.08156 -3.05058 0.18473 H -0.80979 -2.95406 -0.61956 H -0.60914 -2.94033 1.12936 H 0.38067 -4.04480 0.14363 C -0.78047 0.24679 -2.98481 H -1.03283 1.29897 -2.86598 H -1.62037 -0.35203 -2.63533 H -0.58944 0.04912 -4.04763 C 1.47145 2.25585 -2.19394 H 0.57307 2.70453 -2.62879 H 2.31142 2.77545 -2.67222 O -1.75133 -0.14579 -0.12129 O -3.11305 -1.05452 -0.64760