I II - Nature...V 0.0 quartet 1.498 1.777 TS (461 i) 4.1 kcal/mol –121.9 kcal/mol quartet quartet...
Transcript of I II - Nature...V 0.0 quartet 1.498 1.777 TS (461 i) 4.1 kcal/mol –121.9 kcal/mol quartet quartet...
2.536(2.351)
2.279
(2.239)
I'
0.0 (+5.4) kcal/mol
quintet (triplet)
I
0.0 (+4.1) kcal/mol
quintet (triplet)
2.492(2.348)
2.106
(2.077)
2.105
(2.175)
2.360
(2.497)
1.867
(2.005)
1.126
(1.115)
2.356(2.508)
2.276(2.286)
1.857
(2.076)
1.131(1.112)
Fe
O
Si
C
H
Cl
II
0.0 (+4.3) kcal/mol
triplet (quintet)
II'
0.0 (+1.9) kcal/mol
triplet (quintet)
N
Supplementary Figure S1 | Stable structures of I, I', II, and II' optimized at the
B3LYP*/6-311+G** level of theory.
2
Supplementary Figure S2 | Energy profile of a possible catalytic cycle on the
transformation of N2 into N(SiMe3)3 catalyzed by [Fe(SiMe3)2(thf)] (I).
Si represents trimethylsilyl radical. The energy change and activation energy (in parenthesis)
for each reaction step were calculated at the B3LYP*/6-311+G** level of theory. The
energies are presented in kcal/mol.
thf
Fe NSi
Si
thf
Fe NSi
Si
N
Si
Si
thf
Fe NSi2
Si
thf
Fe NSi2Si
Si
Fe thf
Si
Si
thf
Fe NSi3
Si
thf
Fe NSi3
Si
Si
N
thf
Fe NSi
Si
N
Si
–12.1(no barrier)
–21.3(3.1)
SiN2
–36.6(0.9)
Si
–1.6(12.0)
Si
I (triplet) II (triplet) III (quartet) IV (triplet)
X (quintet)
Si
–22.3(0.6)
VII (quintet)
Si migration
+7.6(19.0)
Si
VIII (quartet)
IX (quartet)
–16.6(0.4)
thf
Fe NSi
Si
NSi3
–121.9(4.1)
N–N cleavage
V (quartet)
thf Fe NSi2
VI (quartet)
Si migration
–35.6(no barrier)
–22.3(0.6)
Si
N(SiMe3)3
N(SiMe3)3
3
1.865
1.126
4.443
II – SiMe3 TS (123i) III
O
NNFe
Si
C
2.5311.153
1.819
1.805
1.204
1.742
0.0 3.1 kcal/mol –21.3 kcal/mol
quartet quartet quartet
Supplementary Figure S3 | Energy profile and optimized structures for the addition
of Me3Si radical to II.
4
1.742
1.206
4.930
III – SiMe3 TS (34i) IV
3.199
1.206
1.754
1.814 (1.818)
1.328(1.325)
1.741(1.731)
0.0 0.9 kcal/mol –32.6 (–36.5) kcal/mol
quintet quintet quintet (triplet)
Supplementary Figure S4 | Energy profile and optimized structures for the addition
of Me3Si radical to III.
5
IV – SiMe3 TS (148i) V
0.0 12.0 kcal/mol –1.6 kcal/mol
quartet quartet quartet
2.615
1.343
1.7696.269
1.325
1.732
1.8801.498
1.777
Supplementary Figure S5 | Energy profile and optimized structures for the addition
of Me3Si radical to IV.
6
V
0.0
quartet
1.498
1.777
TS (461i)
4.1 kcal/mol –121.9 kcal/mol
quartet quartet
1.829
1.707
VI – N(SiMe3)3
7.722
1.869
Supplementary Figure S6 | Energy profile and optimized structures for the N-N bond
cleavage of V and the generation of N(SiMe3)3.
7
2.439
6.227
4.532
VII – SiMe3 TS (18i) VIII
0.0 0.6 kcal/mol –22.3 kcal/mol
quartet quartet quartet
Supplementary Figure S7 | Energy profile and optimized structures for the addition
of Me3Si radical to VII.
8
IXTS (150i)VIII
2.152
4.626
19.0 kcal/mol0.0
quartetquartetquartet
2.244
2.336
2.551
7.6 kcal/mol
N–Fe–Si = 170.4°
2.439
1.990
2.208
1.947
1.847
Supplementary Figure S8 | Energy profile and optimized structures for the Me3Si
migration of VIII yielding IX.
9
6.619 4.533
IX – SiMe3 TS (41i) X
0.0 0.3 kcal/mol –23.3 kcal/mol
quintet quintet quintet
5.1274.697 4.834
2.546
Supplementary Figure S9 | Energy profile and optimized structures for the addition
of Me3Si radical to IX.
10
5.127
3.369
X TS (46i) I – N(SiMe3)3
0.0 0.4 kcal/mol –16.6 kcal/mol
quintet quintet quintet
2.378 2.460
2.107 7.654
Supplementary Figure S10 | Energy profile and optimized structures for the release
of N(SiMe3)3 from X.
11
Supplementary Table S1 | [Fe(CO)5]-catalyzed formation of N(SiMe3)3 from N2.a
—————————————————————————————————————————————
Fe(CO)5 solvent temp. amount (mmol)b
equiv of 1 based run ————————————————— (mmol) (mL) (°C) 1 2 3 4 on Fe atom
—————————————————————————————————————————————
1 0.10 THF (40) rt 2.54 0.50 5.09 8.98 25
2 0.03 THF (40) rt 0.09 1.98 0.42 3.02 3
3 0.50 THF (40) rt 6.18 0.78 6.44 3.53 12
4 0.10 THF (20) rt 2.20 0.58 5.22 13.31 22
5 0.10 THF (60) rt 0.77 0.30 2.14 3.78 8
6 0.10 THF (40) 40 2.56 1.30 5.23 21.32 26
7 0.10 THF (40) 60 1.60 1.32 4.73 20.92 16
8c 0.10 THF (40) rt 2.35 3.89 0.89 10.72 24
9 0.10 hexane (40) rt 0 2.15 0 0 0
10 0.10 benzene (40) rt 0 0 0 0 0
11 0.10 Et2O (40) rt 0 0 0 0 0
12 0.10 DME (40) rt 0.18 0 0 0 2
13 0.10 dioxane (40) rt 0.02 0.57 0 0 0.2
14d 0.10 THF (40) rt 0.50 20.66 0.26 0 5
15e 0.10 THF (40) rt 0.03 1.80 0.16 9.62 0.3
16f 0.10 THF (40) rt 0.01 0.62 0.12 1.11 0.1
17g 0.10 THF (40) rt 2.01 0.97 3.41 10.03 20
————————————————————————————————————————————— a All reactions using Na (60 mmol) and Me3SiCl (60 mmol) were carried out in the presence of
[Fe(CO)5] under atmospheric pressure of N2. b Determined by GLC analysis. c For 100 h. d Li was
used in place of Na. e The reaction was carried out under argon atmosphere. f The reaction was
carried out under dry air. g The reaction was carried out in the presence of galvinoxyl (0.10 mmol).
N2 (1 atm)
+ 6 Na(60 mmol)
6 Me3SiCl(60 mmol)
[Fe(CO)5]
(0.10 mmol)
solvent6 NaCl+ +2 N(SiMe3)3
1temp
20 h
2 3
CH3CH2CH2CH2OSiMe3Me3SiSiMe3
4
Me3SiCH2CH2CH2CH2OSiMe3
12
Supplementary Table S2 | Fe-catalyzed formation of N(SiMe3)3 from N2.a
—————————————————————————————————————————————
amount (mmol) b equiv of 1 based run catalyst ———————————————————— 1 2 3 4 on Fe atom
—————————————————————————————————————————————
1 [Fe(CO)5] 2.54 0.50 5.09 8.98 25
2 [Fe2(CO)9] c 0.86 1.34 2.59 7.01 9
3 [Fe3(CO)12] d 1.20 0.26 2.11 5.77 12
4 [Fe(SiMe3)2(CO)4] 2.94 0.69 5.07 8.85 29
5 [CpFe(CO)2]2 e 1.69 0.68 3.38 14.34 17
6 [CpFe(CO)2I] 2.73 0.69 4.74 14.59 27
7 [Cp2Fe] 1.32 1.05 2.17 13.05 13
8 [Cp'2Fe] f 2.32 1.14 3.98 17.01 23
9 [Cp''2Fe] g 3.41 0.28 5.45 4.89 34
————————————————————————————————————————————— a All reactions using Na (60 mmol) and Me3SiCl (60 mmol) were carried out in the presence of a
catalyst (0.10 mmol) under atmospheric pressure of N2 at room temperature for 20 h in THF (40 mL).
b Determined by GLC analysis. c [Fe2(CO)9] (0.05 mmol) was used. d [Fe3(CO)12] (0.033 mmol)
was used. e [CpFe(CO)2]2 (0.05 mmol) was used. f [Cp'2Fe] = [(η5-C5H4SiMe3)2Fe]. g [Cp''2Fe] =
[{η5-C5H2(SiMe3)3}2Fe].
N2 (1 atm)
+ 6 Na(60 mmol)
6 Me3SiCl(60 mmol)
catalyst (0.10 mmol)
THF6 NaCl+ +2 N(SiMe3)3
1rt
20 h
2 3
CH3CH2CH2CH2OSiMe3Me3SiSiMe3
4
Me3SiCH2CH2CH2CH2OSiMe3
13
Supplementary Table S3 | Time profile of [Fe(CO)5]-catalyzed formation of
N(SiMe3)3 from N2.a
—————————————————————————————————————————————
amount (mmol)b t (h) ———————————————————————————————
1 2 3 4
—————————————————————————————————————————————
0 0 0 0 0
2 0.11 0 0 0.40
4 0.34 0 0.11 0.98
6 0.52 0 0.29 1.80
9 0.77 0 0.68 3.47
12 1.06 0.09 0.68 3.91
20 2.21 0.25 2.54 6.96
24 2.26 0.24 2.56 6.96
—————————————————————————————————————————————
a Reaction using Na (60 mmol) and Me3SiCl (60 mmol) were carried out in the
presence of Fe(CO)5 (0.10 mmol) under atmospheric pressure of N2 at room
temperature in THF (40 mL). b Determined by GLC analysis.
N2 (1 atm)
+ 6 Na(60 mmol)
6 Me3SiCl(60 mmol)
[Fe(CO)5]
(0.10 mmol)6 NaCl+ +2 N(SiMe3)3
1
2 3
CH3CH2CH2CH2OSiMe3Me3SiSiMe3
4
Me3SiCH2CH2CH2CH2OSiMe3
THF
rt
20 h
14
Supplementary Table S4 | Cartesian coordinate of I in the triplet state. Units are presented in Å.
SCF energy = -2314.19197075 hartree
ZPE = 0.336802 hartree
--------------------------------------------------------
Atom Coordinates (Angstroms)
X Y Z
--------------------------------------------------------
Fe 6.533813 1.946462 0.314317
C 4.139856 -1.603915 -0.543552
C 5.504317 -2.127785 -1.020134
C 6.317728 -0.844699 -1.172231
O 5.777586 0.071822 -0.164969
C 4.534366 -0.464803 0.391808
H 3.558256 -1.221507 -1.389063
H 3.542489 -2.363935 -0.033690
H 5.443892 -2.686517 -1.957423
H 5.951032 -2.780063 -0.262006
H 7.384407 -0.962853 -0.972232
H 6.181129 -0.377542 -2.152556
H 3.808320 0.350496 0.434083
H 4.743565 -0.818373 1.407408
Si 7.830548 3.029528 1.954344
C 9.706561 2.799075 1.655331
H 10.046037 3.339721 0.766033
H 10.280137 3.172439 2.514643
H 9.964808 1.742235 1.519286
C 7.569536 4.871767 2.385860
H 7.861602 5.532683 1.562965
H 6.520985 5.083821 2.624594
H 8.172736 5.145735 3.261936
C 7.454503 2.082200 3.588314
H 6.413481 2.217953 3.904506
H 7.636947 1.005267 3.489333
H 8.097962 2.452001 4.399282
Si 6.749771 3.697980 -1.234141
C 6.178161 2.991663 -2.931047
H 5.164274 2.577096 -2.879301
H 6.172732 3.785148 -3.691892
H 6.848684 2.200247 -3.287026
C 5.558707 5.143954 -0.856042
H 4.520190 4.799833 -0.786946
H 5.807355 5.641301 0.086645
H 5.607405 5.895068 -1.656318
C 8.463417 4.466647 -1.578331
H 8.848271 5.017455 -0.714042
H 9.204358 3.702770 -1.840285
H 8.397946 5.169809 -2.419722
--------------------------------------------------------
15
Supplementary Table S5 | Cartesian coordinate of I in the quintet state. Units are presented in Å.
SCF energy = -2314.19832292 hartree
ZPE = 0.336693 hartree
--------------------------------------------------------
Atom Coordinates (Angstroms)
X Y Z
--------------------------------------------------------
Fe 6.811259 2.455680 0.089014
C 4.295191 -1.117584 0.718203
C 4.357993 -1.108730 -0.817966
C 4.783323 0.323750 -1.124942
O 5.614737 0.724329 0.016200
C 5.491552 -0.253431 1.102925
H 3.363265 -0.659839 1.067209
H 4.362021 -2.121537 1.144932
H 3.404204 -1.361007 -1.288198
H 5.112208 -1.818134 -1.175401
H 5.383368 0.434508 -2.029321
H 3.931033 1.009441 -1.171843
H 5.371759 0.299579 2.035490
H 6.422718 -0.828334 1.142151
Si 7.985841 2.926390 2.236076
C 9.883342 2.703978 2.101467
H 10.306850 3.344546 1.319155
H 10.378571 2.962397 3.047576
H 10.151919 1.669165 1.857019
C 7.718392 4.727554 2.828326
H 8.062672 5.451214 2.080332
H 6.659348 4.936090 3.021487
H 8.271976 4.921103 3.757325
C 7.452359 1.825059 3.718595
H 6.387899 1.948307 3.954156
H 7.631423 0.760601 3.523370
H 8.020179 2.092178 4.620560
Si 6.939519 3.855583 -1.969187
C 6.257592 3.026921 -3.564053
H 5.189115 2.793119 -3.481162
H 6.379057 3.696112 -4.427155
H 6.788167 2.095160 -3.796015
C 5.982905 5.507050 -1.810837
H 4.910011 5.338054 -1.659219
H 6.343349 6.099540 -0.961809
H 6.099654 6.118294 -2.716311
C 8.742564 4.341954 -2.392963
H 9.217046 4.886947 -1.568657
H 9.360561 3.460112 -2.600018
H 8.775256 4.988218 -3.280851
--------------------------------------------------------
16
Supplementary Table S6 | Cartesian coordinate of I' in the triplet state. Units are presented in Å.
SCF energy = -2542.08429246 hartree
ZPE = 0.219624 hartree
--------------------------------------------------------
Atom Coordinates (Angstroms)
X Y Z
--------------------------------------------------------
Fe -0.073055 -0.970854 -0.001269
Si 0.564427 0.551170 1.672743
C 2.463261 0.590647 1.988444
H 2.849346 -0.420881 2.164010
H 3.010497 1.010412 1.137422
H 2.696682 1.197508 2.875751
C -0.161235 -0.062663 3.352376
H 0.136905 -1.098182 3.553373
H 0.187435 0.564708 4.187272
H -1.257526 -0.036639 3.342336
C 0.042087 2.403795 1.632173
H 0.325594 2.903763 2.569968
H 0.512844 2.949264 0.806357
H -1.044060 2.504119 1.515566
Si 0.522407 0.512116 -1.723922
C 2.172104 1.504055 -1.718639
H 2.201390 2.251769 -0.918193
H 3.032869 0.838658 -1.578052
H 2.307946 2.029993 -2.675063
C -0.830922 1.831886 -2.090959
H -0.935463 2.550351 -1.270754
H -0.586831 2.393507 -3.004808
H -1.807944 1.356694 -2.241060
C 0.633645 -0.492595 -3.368014
H 0.806324 0.174193 -4.226955
H 1.453983 -1.219536 -3.331874
H -0.289952 -1.054317 -3.549445
Cl -0.929140 -3.039190 0.029117
--------------------------------------------------------
17
Supplementary Table S7 | Cartesian coordinate of I' in the quintet state. Units are presented in Å.
SCF energy = -2542.08429246 hartree
ZPE = 0.218947 hartree
--------------------------------------------------------
Atom Coordinates (Angstroms)
X Y Z
--------------------------------------------------------
Fe 0.315298 -0.649656 -0.015796
Si 0.681418 0.568280 2.178797
C 2.482758 0.447087 2.853870
H 2.770534 -0.598462 3.018610
H 3.202772 0.875951 2.145831
H 2.589929 0.982292 3.809601
C -0.400843 -0.054248 3.644226
H -0.233647 -1.122391 3.826709
H -0.175128 0.491738 4.572848
H -1.468852 0.073127 3.428501
C 0.341534 2.465079 2.128782
H 0.526877 2.931349 3.108197
H 0.982010 2.965722 1.392043
H -0.698805 2.673871 1.849548
Si 0.493527 0.543114 -2.246243
C 2.056357 1.659140 -2.412739
H 2.092527 2.412739 -1.616507
H 2.976034 1.065231 -2.340605
H 2.071101 2.187352 -3.378053
C -0.963509 1.749231 -2.619859
H -1.047361 2.521931 -1.845626
H -0.826658 2.255163 -3.587646
H -1.920983 1.214694 -2.652691
C 0.566208 -0.586064 -3.803567
H 0.634116 0.006409 -4.728702
H 1.434748 -1.254695 -3.764215
H -0.325465 -1.220920 -3.869778
Cl -0.152876 -2.879315 0.052364
--------------------------------------------------------
18
Supplementary Table S8 | Cartesian coordinate of II in the triplet state. Units are presented in Å.
SCF energy = -2423.71195298 hartree
ZPE = 0.344771 hartree
--------------------------------------------------------
Atom Coordinates (Angstroms)
X Y Z
--------------------------------------------------------
Fe 0.532224 -0.041515 9.721906
Si 2.128326 -0.683506 11.336733
Si -0.760929 0.998988 11.432620
N 2.434755 1.354023 7.881015
N 1.728042 0.811716 8.569109
C -1.895706 -0.135384 12.471968
H -2.529568 -0.769253 11.840441
H -1.319694 -0.794304 13.129160
H -2.561581 0.469728 13.101959
C -1.950611 2.078304 10.371956
H -2.558128 1.472173 9.689295
H -2.640283 2.625807 11.029536
H -1.409772 2.819143 9.772334
C 0.059411 2.209458 12.655749
H -0.713574 2.750401 13.218103
H 0.699419 1.699363 13.382967
H 0.674400 2.951748 12.135268
C 1.638036 -1.418660 13.026912
H 1.237638 -0.664327 13.712025
H 0.883563 -2.206523 12.922306
H 2.519819 -1.863657 13.507344
C 3.504982 0.587626 11.662618
H 3.132150 1.448256 12.227521
H 4.316788 0.131986 12.245102
H 3.931235 0.963976 10.726766
C 2.912658 -2.146773 10.365702
H 3.746775 -2.559875 10.950054
H 2.199715 -2.962123 10.196291
H 3.312504 -1.837174 9.394098
C -1.759128 -1.520118 6.234437
C -2.683672 -1.948783 7.386059
C -1.743158 -1.922536 8.588026
O -0.766646 -0.876365 8.291687
C -0.883633 -0.460017 6.894752
H -1.149977 -2.365393 5.896167
H -2.302527 -1.124986 5.372367
H -3.130010 -2.934923 7.234909
H -3.494098 -1.223661 7.517195
H -2.229038 -1.667867 9.531855
H -1.198378 -2.865925 8.706015
H 0.124847 -0.389351 6.483482
H -1.351699 0.530390 6.875144
--------------------------------------------------------
19
Supplementary Table S9 | Cartesian coordinate of II in the quintet state. Units are presented in Å.
SCF energy = -2423.70380027 hartree
ZPE = 0.343529 hartree
--------------------------------------------------------
Atom Coordinates (Angstroms)
X Y Z
--------------------------------------------------------
Fe 0.547454 0.378988 9.785442
Si 2.184120 -1.055532 11.010582
Si -0.922889 1.687333 11.324706
N 1.757679 2.066839 7.469245
N 1.270163 1.403085 8.220402
C -2.245471 0.589949 12.168374
H -2.950167 0.172157 11.439118
H -1.790346 -0.247609 12.708800
H -2.829306 1.175823 12.891441
C -1.881285 3.118944 10.487347
H -2.556768 2.753413 9.704956
H -2.489497 3.661754 11.224309
H -1.199288 3.841401 10.024219
C 0.094822 2.480713 12.733708
H -0.559419 3.039961 13.416335
H 0.624214 1.724895 13.324632
H 0.844675 3.178770 12.344363
C 1.373984 -1.986699 12.472156
H 0.921023 -1.291570 13.187860
H 0.586736 -2.672807 12.137574
H 2.122480 -2.581043 13.013827
C 3.593441 -0.004261 11.759772
H 3.204260 0.765728 12.435279
H 4.286545 -0.634211 12.333912
H 4.173962 0.503647 10.980906
C 3.029600 -2.393666 9.930262
H 3.734682 -2.987935 10.527886
H 2.299672 -3.086026 9.494144
H 3.592059 -1.943874 9.103814
C -2.043098 -1.715735 6.742596
C -1.890618 -2.795028 7.827309
C -1.472442 -1.973846 9.042557
O -0.689590 -0.867406 8.502831
C -0.893543 -0.762303 7.063178
H -1.976308 -2.113851 5.726851
H -3.006252 -1.204291 6.845436
H -1.102898 -3.505670 7.554579
H -2.810855 -3.357000 8.006159
H -2.334446 -1.555909 9.574618
H -0.840062 -2.510796 9.752181
H 0.037926 -1.058810 6.567640
H -1.109467 0.282564 6.827649
--------------------------------------------------------
20
Supplementary Table S10 | Cartesian coordinate of II' in the triplet state. Units are presented in Å.
SCF energy = -2651.59805008 hartree
ZPE = 0.227780 hartree
--------------------------------------------------------
Atom Coordinates (Angstroms)
X Y Z
--------------------------------------------------------
Fe -0.239244 -0.957871 0.011947
Si 0.585459 0.611459 1.573098
C 2.449497 0.458654 1.984490
H 2.718807 -0.595374 2.114254
H 3.076939 0.866314 1.184130
H 2.693310 0.994991 2.913272
C -0.329518 -0.022485 3.145107
H -0.143546 -1.089660 3.304160
H 0.023205 0.528312 4.030169
H -1.413553 0.121528 3.068359
C 0.219658 2.496272 1.576208
H 0.512219 2.932410 2.542404
H 0.761091 3.035623 0.791201
H -0.850467 2.686145 1.431906
Si 0.358688 0.662659 -1.590592
C 2.100480 1.468124 -1.670171
H 2.251124 2.227112 -0.894494
H 2.884292 0.711223 -1.547861
H 2.249796 1.953659 -2.645490
C -0.858496 2.079041 -2.007948
H -0.848599 2.859169 -1.238968
H -0.594617 2.547687 -2.966863
H -1.884409 1.701854 -2.083798
C 0.340908 -0.493985 -3.136650
H 0.673773 0.063753 -4.024818
H 1.008434 -1.354372 -3.011551
H -0.664951 -0.879991 -3.336035
Cl 0.438363 -3.039253 0.636780
N -2.045122 -0.802406 -0.393324
N -3.155671 -0.736971 -0.597427
--------------------------------------------------------
21
Supplementary Table S11 | Cartesian coordinate of II' in the quintet state. Units are presented in Å.
SCF energy = -2651.59288392 hartree
ZPE = 0.225694 hartree
--------------------------------------------------------
Atom Coordinates (Angstroms)
X Y Z
--------------------------------------------------------
Fe -0.037825 -0.490354 0.026511
Si 0.283580 0.800435 2.152127
C 2.119922 1.258496 2.511367
H 2.745370 0.358884 2.562753
H 2.532921 1.897140 1.720710
H 2.220670 1.796238 3.466245
C -0.273441 -0.142236 3.736282
H 0.232647 -1.111771 3.812234
H -0.049644 0.433723 4.647147
H -1.352599 -0.339755 3.719445
C -0.634114 2.492119 2.278751
H -0.428637 2.983971 3.241395
H -0.322654 3.176075 1.479718
H -1.721016 2.366478 2.193560
Si 0.453647 0.686547 -2.133517
C 2.333945 0.959232 -2.449682
H 2.782435 1.584588 -1.667784
H 2.872283 0.003517 -2.450070
H 2.513734 1.449462 -3.418395
C -0.302587 2.448332 -2.337367
H 0.044189 3.125079 -1.546657
H -0.025450 2.892096 -3.305497
H -1.398458 2.421780 -2.284638
C -0.143485 -0.252868 -3.705528
H 0.153043 0.273006 -4.625874
H 0.278540 -1.264220 -3.740356
H -1.235879 -0.356120 -3.714471
Cl 0.436888 -2.725261 0.104464
N -2.112085 -0.509328 -0.057203
N -3.215550 -0.381073 -0.107152
--------------------------------------------------------
22
Supplementary Table S12 | Cartesian coordinate of II-SiMe3 in the quartet state. Units are presented in Å.
SCF energy = -2832.81357717 hartree
ZPE = 0.453505 hartree
--------------------------------------------------------
Atom Coordinates (Angstroms)
X Y Z
--------------------------------------------------------
Fe 0.702045 0.308253 10.108866
Si 2.034296 -0.631564 11.817757
Si -0.967173 0.860788 11.727462
N 2.029851 1.420821 9.417707
N 2.816656 2.112655 9.005173
C -2.156738 -0.535143 12.267652
H -2.606987 -1.049176 11.409780
H -1.646855 -1.290582 12.874019
H -2.978594 -0.122234 12.868059
C -2.044926 2.097196 10.720992
H -2.474500 1.635466 9.823886
H -2.880003 2.454232 11.339804
H -1.471344 2.975609 10.403943
C -0.473623 1.798608 13.311192
H -1.371359 2.166201 13.826228
H 0.076061 1.166431 14.016013
H 0.157291 2.663268 13.078189
C 1.299122 -1.770032 13.158920
H 0.732250 -1.217092 13.914947
H 0.629709 -2.520701 12.724339
H 2.107607 -2.302790 13.677548
C 3.213088 0.573829 12.698855
H 2.674607 1.232499 13.388258
H 3.959056 0.018524 13.283048
H 3.748633 1.207336 11.983789
C 3.111864 -1.786395 10.720674
H 3.820602 -2.330330 11.360703
H 2.515720 -2.536044 10.187265
H 3.694536 -1.227921 9.980409
C -1.027533 -0.242983 6.071289
C -2.043863 -0.997604 6.943523
C -1.236080 -1.296316 8.203314
O -0.291639 -0.188416 8.327376
C -0.278258 0.603270 7.095335
H -0.344003 -0.944998 5.581506
H -1.495638 0.370494 5.297506
H -2.422410 -1.908604 6.472862
H -2.899037 -0.355019 7.179606
H -1.829474 -1.333853 9.118929
H -0.656786 -2.222089 8.111005
H 0.761989 0.805049 6.833357
H -0.788882 1.550873 7.299106
Si 2.708080 2.701035 4.602592
C 4.305779 1.687076 4.694763
H 4.551879 1.429394 5.729878
H 4.224920 0.756834 4.122738
H 5.148476 2.260816 4.283365
C 2.278341 3.107815 2.800375
H 2.180552 2.198815 2.197661
23
H 1.336933 3.662620 2.728687
H 3.065690 3.726561 2.346657
C 2.850023 4.278944 5.637750
H 1.930493 4.871917 5.593173
H 3.052241 4.044050 6.687581
H 3.672206 4.907613 5.267017
--------------------------------------------------------
24
Supplementary Table S13 | Cartesian coordinate of TS between II-SiMe3 and III in the quartet state. Units are presented in Å.
SCF energy = -2832.80853469 hartree
ZPE = 0.453370 hartree
Imaginary frequency: 123i
--------------------------------------------------------
Atom Coordinates (Angstroms)
X Y Z
--------------------------------------------------------
Fe 0.634699 0.039720 9.550183
Si 2.104530 -0.541020 11.327280
Si -0.829145 1.162011 11.084188
N 1.917793 0.802776 8.450685
N 2.790819 1.190335 7.823344
C -2.042120 0.065218 12.072646
H -2.596124 -0.621476 11.421782
H -1.525110 -0.538340 12.825128
H -2.780784 0.689187 12.593806
C -1.925832 2.188040 9.883879
H -2.481670 1.549086 9.187465
H -2.661998 2.770060 10.455696
H -1.332700 2.893819 9.291654
C -0.101872 2.419790 12.315998
H -0.910208 2.986592 12.797158
H 0.479666 1.933893 13.105898
H 0.556256 3.135209 11.811189
C 1.431036 -1.248063 12.964945
H 0.909667 -0.495298 13.565210
H 0.732626 -2.073738 12.787682
H 2.260150 -1.637929 13.570898
C 3.366493 0.811770 11.767905
H 2.893922 1.659530 12.274692
H 4.138528 0.409931 12.437672
H 3.863965 1.194579 10.870610
C 3.071436 -1.985670 10.513718
H 3.822149 -2.367056 11.220031
H 2.418378 -2.825280 10.248257
H 3.596925 -1.665853 9.607720
C -1.512584 -1.487867 5.984546
C -2.451499 -1.956364 7.108406
C -1.531396 -1.948157 8.326012
O -0.574343 -0.873439 8.077229
C -0.663746 -0.431177 6.685670
H -0.886030 -2.316798 5.637691
H -2.045996 -1.079854 5.122171
H -2.883419 -2.943546 6.925285
H -3.272300 -1.243786 7.243890
H -2.038700 -1.734781 9.269075
H -0.969179 -2.883905 8.423078
H 0.353399 -0.339517 6.300377
H -1.142842 0.553902 6.675514
Si 2.935333 3.102634 6.121235
C 3.988694 2.066516 4.937660
H 4.608917 1.358135 5.496181
H 3.367392 1.494513 4.239739
H 4.655678 2.705781 4.343167
C 1.773980 4.241798 5.129332
25
H 1.122789 3.666957 4.462176
H 1.136391 4.837361 5.791229
H 2.356046 4.939330 4.509221
C 4.044664 4.141368 7.248362
H 3.453873 4.764212 7.928416
H 4.693517 3.501792 7.855161
H 4.684778 4.808076 6.654288
--------------------------------------------------------
26
Supplementary Table S14 | Cartesian coordinate of III in the quartet state. Units are presented in Å.
SCF energy = -2832.85003696 hartree
ZPE = 0.456032 hartree
--------------------------------------------------------
Atom Coordinates (Angstroms)
X Y Z
--------------------------------------------------------
Fe -0.294114 -0.417058 0.235675
Si 1.289653 -1.684469 1.639215
Si -1.557397 1.237044 1.578419
N 0.800427 0.337256 -0.889973
N 1.712767 0.835497 -1.497041
C -3.032932 0.449554 2.517179
H -3.790483 0.060875 1.825411
H -2.711815 -0.377949 3.159855
H -3.527631 1.194867 3.155437
C -2.324865 2.662101 0.552131
H -2.998988 2.282451 -0.224782
H -2.904353 3.340872 1.193299
H -1.550203 3.256580 0.053849
C -0.479415 2.078122 2.913994
H -1.066336 2.819009 3.473968
H -0.088859 1.349886 3.633406
H 0.380201 2.595353 2.472992
C 0.504289 -2.522381 3.169287
H 0.031685 -1.787226 3.830328
H -0.263983 -3.251007 2.884421
H 1.266290 -3.056209 3.754000
C 2.671499 -0.541715 2.287158
H 2.270266 0.245701 2.934570
H 3.409651 -1.110792 2.868439
H 3.198469 -0.054377 1.458785
C 2.149827 -3.078703 0.649693
H 2.870285 -3.617248 1.280798
H 1.429256 -3.813088 0.270116
H 2.695258 -2.672846 -0.209734
C -2.291758 -3.130164 -2.668419
C -3.330669 -3.119107 -1.534386
C -2.509543 -2.625063 -0.348032
O -1.541843 -1.700394 -0.923736
C -1.454803 -1.886469 -2.368629
H -1.673115 -4.032173 -2.610271
H -2.742500 -3.091405 -3.663437
H -3.773864 -4.100955 -1.349335
H -4.139469 -2.415123 -1.758777
H -3.083327 -2.078504 0.403015
H -1.959433 -3.438464 0.139425
H -0.398975 -1.985158 -2.629375
H -1.861269 -0.986672 -2.842958
Si 1.892900 2.486728 -2.203353
C 3.328557 2.335273 -3.399076
H 4.232770 1.996875 -2.882233
H 3.106775 1.613769 -4.192753
H 3.549819 3.298935 -3.872298
C 0.296294 2.960831 -3.078977
H 0.083856 2.280645 -3.910966
27
H -0.554914 2.933158 -2.390489
H 0.364805 3.976401 -3.486949
C 2.280735 3.654275 -0.783269
H 1.458284 3.682390 -0.060768
H 3.185837 3.341351 -0.252555
H 2.440846 4.674464 -1.152311
--------------------------------------------------------
28
Supplementary Table S15 | Cartesian coordinate of III-SiMe3 in the quintet state. Units are presented in Å.
SCF energy = -3241.95129415 hartree
ZPE = 0.564990 hartree
--------------------------------------------------------
Atom Coordinates (Angstroms)
X Y Z
--------------------------------------------------------
Fe 0.993234 0.603494 9.390072
Si 2.178828 -0.840627 11.002481
Si -0.534265 2.124877 10.606824
N 2.299825 1.452564 8.611283
N 3.312335 1.999105 8.251345
C -2.141630 1.235524 11.154861
H -2.716645 0.872240 10.294363
H -1.928539 0.375012 11.799034
H -2.790548 1.921470 11.716889
C -1.116307 3.634256 9.580165
H -1.608782 3.327777 8.649758
H -1.831396 4.244140 10.149630
H -0.271507 4.278224 9.309924
C 0.238024 2.842109 12.200878
H -0.470673 3.511110 12.708061
H 0.510383 2.049341 12.906409
H 1.146374 3.416945 11.987189
C 1.059726 -1.599157 12.356043
H 0.540784 -0.823504 12.930216
H 0.295759 -2.260005 11.929588
H 1.655088 -2.194311 13.062188
C 3.530347 0.154943 11.907232
H 3.101467 0.991220 12.470470
H 4.078741 -0.480745 12.615503
H 4.253110 0.569593 11.195373
C 3.058139 -2.316453 10.157678
H 3.598896 -2.921076 10.899090
H 2.346326 -2.976625 9.647873
H 3.783409 -1.969876 9.413405
C -0.739491 -1.201857 5.700182
C -1.148551 -2.217569 6.780102
C -1.111419 -1.371394 8.047859
O -0.023899 -0.426765 7.833022
C 0.318128 -0.359465 6.413229
H -0.342216 -1.673404 4.797769
H -1.597732 -0.584405 5.413292
H -0.416144 -3.029629 6.842129
H -2.134244 -2.656718 6.605541
H -2.038841 -0.804655 8.192080
H -0.888875 -1.931287 8.958461
H 1.326809 -0.768424 6.290763
H 0.318330 0.693133 6.120798
Si 3.589249 3.730820 7.814039
C 3.583883 4.722978 9.409528
H 4.335419 4.345498 10.110659
H 3.807732 5.777787 9.209533
H 2.607503 4.674068 9.902626
C 2.224018 4.286919 6.643985
H 1.237449 4.151341 7.100108
29
H 2.334276 5.348645 6.392987
H 2.247822 3.718792 5.707627
C 5.271547 3.751161 6.987018
H 5.553442 4.770362 6.698091
H 6.043471 3.366638 7.662004
H 5.278381 3.132503 6.083242
Si 4.294625 -1.373276 4.792588
C 4.466954 0.147683 3.672049
H 5.523231 0.325216 3.424113
H 3.921274 0.018190 2.731477
H 4.084418 1.048489 4.163036
C 5.220907 -1.117831 6.421534
H 6.292514 -0.963786 6.229359
H 4.846176 -0.244442 6.965878
H 5.121235 -1.990009 7.075826
C 4.907869 -2.925928 3.893762
H 5.973435 -2.828688 3.641218
H 4.794040 -3.818937 4.516972
H 4.358294 -3.093151 2.961539
--------------------------------------------------------
30
Supplementary Table S16 | Cartesian coordinate of TS between III-SiMe3 and IV in the quintet state. Units are presented in Å.
SCF energy = -3241.94959875 hartree
ZPE = 0.564730 hartree
Imaginary frequency: 34i
--------------------------------------------------------
Atom Coordinates (Angstroms)
X Y Z
--------------------------------------------------------
Fe 1.061362 0.385560 9.121851
Si 2.315033 -1.158830 10.595019
Si -0.300337 1.911587 10.532220
N 2.287909 1.225535 8.191560
N 3.237368 1.788488 7.706922
C -1.869986 1.025147 11.185851
H -2.525768 0.713098 10.363710
H -1.622345 0.132511 11.771099
H -2.451449 1.697863 11.831495
C -0.960558 3.468703 9.629752
H -1.573829 3.199139 8.761458
H -1.585702 4.072862 10.301983
H -0.146067 4.107303 9.270013
C 0.630240 2.538719 12.077509
H -0.013230 3.197830 12.676053
H 0.942047 1.706129 12.717705
H 1.531669 3.101807 11.811189
C 1.245258 -1.945509 11.974462
H 0.783564 -1.185349 12.614502
H 0.437651 -2.561359 11.561017
H 1.858947 -2.592969 12.615950
C 3.731669 -0.230898 11.476647
H 3.348713 0.576103 12.111231
H 4.309652 -0.913148 12.114732
H 4.421004 0.217755 10.752155
C 3.125598 -2.631901 9.677164
H 3.651345 -3.283627 10.388859
H 2.383955 -3.246001 9.152547
H 3.855170 -2.290054 8.935092
C -1.584725 -0.867126 5.771976
C -1.686812 -2.109110 6.673353
C -1.207750 -1.575932 8.020248
O -0.225028 -0.549052 7.691986
C -0.310256 -0.195297 6.278066
H -1.524665 -1.113161 4.708655
H -2.450671 -0.213413 5.922545
H -1.018256 -2.899311 6.314991
H -2.699227 -2.517269 6.729136
H -2.015523 -1.105726 8.592218
H -0.713491 -2.322473 8.645581
H 0.587778 -0.578440 5.783537
H -0.322777 0.894548 6.207534
Si 3.437928 3.569513 7.415101
C 3.274201 4.421713 9.081373
H 4.064080 4.100120 9.768233
H 3.347294 5.510051 8.969137
H 2.309868 4.194463 9.546102
C 2.089601 4.110323 6.219829
31
H 1.096042 3.911027 6.635803
H 2.157781 5.185678 6.016235
H 2.175903 3.581305 5.264704
C 5.148696 3.795835 6.689964
H 5.353291 4.860306 6.524240
H 5.918145 3.406088 7.364578
H 5.243631 3.276613 5.731314
Si 4.906718 -0.012322 5.656103
C 5.849791 -0.101150 4.005124
H 6.318516 -1.088322 3.881459
H 5.183225 0.060908 3.151291
H 6.644383 0.651212 3.957464
C 6.112424 -0.281172 7.091320
H 6.583180 -1.271924 7.021632
H 6.911523 0.467944 7.085258
H 5.595969 -0.215523 8.053430
C 3.544940 -1.332063 5.677186
H 3.981590 -2.340653 5.675479
H 2.923765 -1.238775 6.573511
H 2.901563 -1.245757 4.794407
--------------------------------------------------------
32
Supplementary Table S17 | Cartesian coordinate of IV in the quintet state. Units are presented in Å.
SCF energy = -3242.00598547 hartree
ZPE = 0.567734 hartree
--------------------------------------------------------
Atom Coordinates (Angstroms)
X Y Z
--------------------------------------------------------
Fe -0.780883 -1.630526 -0.148185
Si -0.171575 0.230997 1.374778
C 1.454557 -0.137175 2.321961
H 1.366563 -1.025554 2.958604
H 2.295593 -0.296092 1.636764
H 1.714893 0.708503 2.973487
C -1.473903 0.612812 2.717110
H -1.618178 -0.241307 3.388625
H -1.164303 1.470396 3.329862
H -2.445380 0.850263 2.270192
C 0.138463 1.865647 0.439199
H 0.406717 2.660369 1.148678
H 0.958743 1.770275 -0.280317
H -0.748888 2.197115 -0.110134
Si 0.340683 -1.327746 -2.362509
C 2.249249 -1.227262 -2.209431
H 2.558020 -0.396894 -1.564233
H 2.671149 -2.147004 -1.785683
H 2.713423 -1.074961 -3.193752
C -0.191906 0.271599 -3.259898
H 0.012975 1.158861 -2.651292
H 0.352081 0.382136 -4.207889
H -1.263392 0.269316 -3.488413
C 0.012403 -2.759670 -3.596792
H 0.499015 -2.559112 -4.561487
H 0.405765 -3.714238 -3.225563
H -1.058878 -2.894261 -3.784569
N -2.521369 -1.614428 -0.147284
N -3.837214 -1.563435 0.020977
Si -4.508525 -2.853649 1.101419
Si -4.615331 -0.392878 -1.125513
C -3.828307 1.294560 -0.889149
H -2.753837 1.254360 -1.084961
H -4.272159 2.018676 -1.582813
H -3.976705 1.669468 0.129175
C -6.473653 -0.277205 -0.818756
H -6.719158 0.079215 0.186016
H -6.889222 0.444137 -1.533737
H -6.992265 -1.227187 -0.984490
C -4.327404 -1.040268 -2.869462
H -4.677223 -0.321205 -3.619655
H -3.263064 -1.222403 -3.044323
H -4.863524 -1.982060 -3.032907
C -4.780191 -4.412105 0.070090
H -5.583085 -4.270424 -0.662300
H -3.873048 -4.680146 -0.482147
H -5.056677 -5.264191 0.703021
C -6.140129 -2.317397 1.879672
H -6.959459 -2.236149 1.161202
33
H -6.431207 -3.067698 2.625557
H -6.045515 -1.358721 2.400818
C -3.266730 -3.166876 2.475887
H -3.644630 -3.951223 3.143202
H -2.292157 -3.476969 2.090527
H -3.114949 -2.261223 3.072774
C 0.561211 -5.886099 0.210392
C 1.811936 -5.019244 0.429355
C 1.235022 -3.806577 1.150105
O -0.090619 -3.620436 0.574610
C -0.522989 -4.848091 -0.089046
H 0.673985 -6.605204 -0.605134
H 0.320248 -6.443196 1.122393
H 2.247640 -4.719650 -0.529787
H 2.585555 -5.521644 1.016067
H 1.120311 -3.986873 2.226091
H 1.794207 -2.880963 1.001201
H -0.610827 -4.631613 -1.158215
H -1.506216 -5.117702 0.304190
--------------------------------------------------------
34
Supplementary Table S18 | Cartesian coordinate of IV in the triplet state. Units are presented in Å.
SCF energy = -3242.01320199 hartree
ZPE = 0.568718 hartree
--------------------------------------------------------
Atom Coordinates (Angstroms)
X Y Z
--------------------------------------------------------
Fe -0.836668 -1.757874 -0.095339
Si 0.189795 -0.352418 1.586574
C 1.912135 0.471429 1.448073
H 2.710858 -0.266459 1.308260
H 1.978021 1.188053 0.623673
H 2.128760 1.015007 2.377905
C 0.363995 -1.433348 3.171739
H 1.145684 -2.194893 3.056809
H 0.647792 -0.805195 4.027615
H -0.563648 -1.953331 3.433725
C -1.007907 1.067086 2.046375
H -0.614724 1.638813 2.897941
H -1.143138 1.761323 1.210140
H -1.997443 0.689934 2.326746
Si 0.207632 -0.514709 -1.858652
C 2.095083 -0.838641 -1.943011
H 2.626134 -0.543790 -1.034699
H 2.309555 -1.896947 -2.133845
H 2.520406 -0.268887 -2.780777
C -0.022941 1.381841 -1.892510
H 0.422377 1.871369 -1.020530
H 0.449471 1.803995 -2.789852
H -1.083092 1.658851 -1.917347
C -0.388236 -1.111784 -3.582816
H 0.202424 -0.619467 -4.368334
H -0.254918 -2.193859 -3.699548
H -1.441629 -0.884725 -3.771373
N -2.542163 -1.995363 -0.273845
N -3.860975 -1.873294 -0.324271
Si -4.767104 -1.816943 1.252903
Si -4.506046 -1.648604 -2.008965
C -4.029200 0.075718 -2.585740
H -2.964942 0.264942 -2.426931
H -4.242204 0.209870 -3.652902
H -4.592315 0.837187 -2.034233
C -6.389595 -1.786747 -2.025668
H -6.884665 -1.060100 -1.373091
H -6.732218 -1.582750 -3.048167
H -6.740991 -2.787611 -1.758137
C -3.784569 -3.007456 -3.087344
H -4.074146 -2.864828 -4.135089
H -2.693354 -3.012422 -3.033781
H -4.152280 -3.989644 -2.768616
C -6.214707 -3.028627 1.212207
H -7.025056 -2.716435 0.549118
H -5.888445 -4.028736 0.905360
H -6.632976 -3.115560 2.222832
C -5.397402 -0.061449 1.527480
H -6.074562 0.261433 0.729219
35
H -5.947497 0.008997 2.473825
H -4.566198 0.650608 1.569259
C -3.606532 -2.331217 2.631940
H -4.148683 -2.307490 3.585424
H -3.234110 -3.349681 2.481377
H -2.743704 -1.667526 2.711732
C 0.394868 -6.037762 -0.014717
C 1.600731 -5.398624 0.694138
C 1.519196 -3.949907 0.224043
O 0.095687 -3.682188 0.072818
C -0.656928 -4.931682 0.058216
H 0.641975 -6.265515 -1.057399
H 0.055091 -6.960375 0.463142
H 2.552614 -5.865452 0.427978
H 1.482988 -5.456315 1.781768
H 1.918488 -3.222229 0.932883
H 2.002413 -3.804808 -0.748483
H -1.337311 -4.901907 -0.795343
H -1.243217 -4.979111 0.982298
--------------------------------------------------------
36
Supplementary Table S19 | Cartesian coordinate of IV-SiMe3 in the quartet state. Units are presented in Å.
SCF energy = -3651.113779 hartree
ZPE = 0.677474 hartree
--------------------------------------------------------
Atom Coordinates (Angstroms)
X Y Z
--------------------------------------------------------
Fe -0.536074 -1.304717 -0.014597
Si 0.336457 0.230548 1.638147
C 1.970083 1.218908 1.494119
H 2.839187 0.560194 1.380968
H 1.973598 1.917596 0.651686
H 2.121104 1.804425 2.411349
C 0.592314 -0.782462 3.255427
H 1.456782 -1.453497 3.177883
H 0.783584 -0.105030 4.099369
H -0.278223 -1.395795 3.510979
C -1.003850 1.535549 2.042440
H -0.694760 2.150023 2.898991
H -1.176282 2.206118 1.193906
H -1.963062 1.070319 2.294368
Si 0.403554 -0.005474 -1.791835
C 2.311688 -0.187919 -1.861543
H 2.812304 0.138863 -0.946571
H 2.603186 -1.227114 -2.056283
H 2.702580 0.415770 -2.692341
C 0.027198 1.866395 -1.854378
H 0.434427 2.399145 -0.989355
H 0.466074 2.310816 -2.757936
H -1.051097 2.061384 -1.880777
C -0.135301 -0.671109 -3.509300
H 0.423533 -0.150585 -4.299835
H 0.075668 -1.742625 -3.606334
H -1.201134 -0.523612 -3.706737
N -2.210414 -1.706345 -0.199436
N -3.533414 -1.725311 -0.259658
Si -4.458770 -1.787744 1.306549
Si -4.190512 -1.580091 -1.947591
C -3.888268 0.179340 -2.537575
H -2.842731 0.467754 -2.404936
H -4.136579 0.286641 -3.600238
H -4.507390 0.888151 -1.975928
C -6.050784 -1.906805 -1.960093
H -6.610948 -1.251439 -1.285341
H -6.421284 -1.712850 -2.974692
H -6.295629 -2.944758 -1.715979
C -3.337866 -2.864375 -3.020987
H -3.673605 -2.779232 -4.061393
H -2.253133 -2.736283 -3.003832
H -3.573960 -3.876430 -2.672980
C -5.704693 -3.206435 1.258200
H -6.545884 -3.017677 0.586205
H -5.228365 -4.144709 0.951450
H -6.115911 -3.357195 2.264293
C -5.354305 -0.145583 1.549377
H -6.064780 0.060639 0.741493
37
H -5.918437 -0.148904 2.490118
H -4.641697 0.685357 1.589413
C -3.254262 -2.094592 2.708950
H -3.811921 -2.157944 3.651639
H -2.711718 -3.035409 2.573159
H -2.518071 -1.293551 2.800128
C 1.019381 -5.468394 -0.038425
C 2.147677 -4.790363 0.756307
C 1.976290 -3.324097 0.371178
O 0.543650 -3.151117 0.171505
C -0.113719 -4.448948 0.062463
H 1.318998 -5.607948 -1.082912
H 0.733717 -6.442815 0.366534
H 3.141031 -5.169537 0.502557
H 1.994091 -4.924572 1.832655
H 2.292257 -2.617521 1.141175
H 2.487059 -3.083385 -0.567667
H -0.770965 -4.417404 -0.808588
H -0.720392 -4.593332 0.963081
Si -5.115003 -7.732417 -1.102437
C -4.702990 -8.717472 0.464605
H -5.125477 -8.243600 1.356733
H -5.114356 -9.734918 0.399553
H -3.621234 -8.804375 0.610391
C -6.992170 -7.589383 -1.319324
H -7.456919 -7.094594 -0.460275
H -7.248983 -7.017110 -2.216740
H -7.445147 -8.586302 -1.417236
C -4.327441 -8.542560 -2.624491
H -4.541180 -7.973117 -3.534922
H -3.239680 -8.614556 -2.521707
H -4.718373 -9.560263 -2.766095
--------------------------------------------------------
38
Supplementary Table S20 | Cartesian coordinate of TS between IV-SiMe3 and V in the quartet state. Units are presented in Å.
SCF energy = -3651.096630 hartree
ZPE = 0.679459 hartree
Imaginary frequency: 148i
--------------------------------------------------------
Atom Coordinates (Angstroms)
X Y Z
--------------------------------------------------------
Fe -0.885252 -1.927095 -0.226947
Si 0.148311 -0.494436 1.470431
C 1.904137 0.248217 1.289085
H 2.664669 -0.523964 1.123015
H 1.978501 0.965547 0.466039
H 2.172006 0.776361 2.214465
C 0.298711 -1.537446 3.082537
H 1.022854 -2.353673 2.970910
H 0.649734 -0.900901 3.906649
H -0.654872 -1.978701 3.393497
C -0.974448 0.981200 1.938226
H -0.497350 1.586256 2.721221
H -1.169626 1.635283 1.082417
H -1.940447 0.641860 2.327407
Si 0.068394 -0.588027 -2.002504
C 1.954301 -0.871317 -2.195927
H 2.521173 -0.636919 -1.291270
H 2.173997 -1.906873 -2.480067
H 2.331308 -0.226934 -3.002099
C -0.174751 1.307528 -1.917882
H 0.357665 1.760924 -1.075595
H 0.202535 1.772582 -2.838842
H -1.232168 1.578720 -1.820627
C -0.605731 -1.073437 -3.730173
H -0.035180 -0.543914 -4.506174
H -0.502392 -2.148302 -3.916879
H -1.660233 -0.812410 -3.859736
N -2.556051 -2.471415 -0.434436
N -3.883893 -2.667725 -0.477950
Si -4.660505 -2.367658 1.174003
Si -4.595724 -1.957659 -2.031277
C -4.164374 -0.129340 -2.099662
H -3.086284 0.030537 -2.030539
H -4.508113 0.285888 -3.055194
H -4.644860 0.440351 -1.299149
C -6.478616 -2.116023 -2.032922
H -6.958899 -1.420164 -1.338076
H -6.828908 -1.855276 -3.040057
H -6.835090 -3.125643 -1.814455
C -3.890974 -2.835463 -3.533966
H -4.062098 -2.207156 -4.416506
H -2.814439 -2.987574 -3.440826
H -4.370412 -3.800132 -3.719948
C -6.410941 -3.069682 1.297674
H -7.119922 -2.568691 0.634610
H -6.469726 -4.144773 1.108798
H -6.756026 -2.901424 2.326624
C -4.760917 -0.505253 1.440086
39
H -5.544062 -0.039124 0.833172
H -4.998067 -0.299007 2.490976
H -3.810853 -0.015606 1.210233
C -3.582234 -3.128729 2.505617
H -3.989258 -2.853007 3.486243
H -3.554023 -4.219035 2.451256
H -2.560880 -2.749076 2.439737
C 1.028099 -5.859915 1.002410
C 2.269793 -4.973791 0.815928
C 1.767292 -3.902514 -0.152001
O 0.339763 -3.777987 0.105814
C -0.101375 -4.833458 1.003542
H 0.918480 -6.550015 0.158325
H 1.053418 -6.448136 1.923764
H 3.131613 -5.515830 0.417824
H 2.563065 -4.522374 1.769944
H 2.225044 -2.922493 -0.005081
H 1.895345 -4.201199 -1.198661
H -1.050862 -5.212889 0.623696
H -0.258260 -4.401011 1.998646
Si -4.318439 -5.216754 -0.870548
C -4.278283 -6.244314 0.732326
H -5.143326 -6.080546 1.381727
H -4.276059 -7.307101 0.450347
H -3.373406 -6.062071 1.319292
C -5.795066 -5.852818 -1.890931
H -6.736271 -5.737118 -1.342680
H -5.900318 -5.341099 -2.851805
H -5.662849 -6.924513 -2.096942
C -2.676486 -5.462296 -1.762182
H -2.807613 -5.528926 -2.845684
H -2.011594 -4.612598 -1.551666
H -2.183074 -6.380266 -1.420604
--------------------------------------------------------
40
Supplementary Table S21 | Cartesian coordinate of V in the quartet state. Units are presented in Å.
SCF energy = -3651.121033 hartree
ZPE = 0.682171 hartree
--------------------------------------------------------
Atom Coordinates (Angstroms)
X Y Z
--------------------------------------------------------
Fe 0.986199 0.422019 0.122292
Si 1.764917 2.257138 1.536158
C 3.598424 2.819150 1.519091
H 4.288549 1.994206 1.731453
H 3.888749 3.250377 0.555522
H 3.758663 3.587065 2.288319
C 1.468190 1.744929 3.369083
H 2.034613 0.847935 3.646573
H 1.780020 2.553771 4.044736
H 0.410732 1.536394 3.566961
C 0.772824 3.882615 1.327351
H 1.126180 4.626638 2.054299
H 0.895152 4.309159 0.326840
H -0.300179 3.742798 1.498183
Si 2.225315 1.260481 -1.788832
C 4.096209 0.846911 -1.679053
H 4.582165 1.309172 -0.814465
H 4.266666 -0.235313 -1.629591
H 4.604756 1.214579 -2.581156
C 2.148949 3.127366 -2.211541
H 2.601029 3.749905 -1.432385
H 2.689202 3.322179 -3.148144
H 1.117540 3.472587 -2.348915
C 1.690840 0.411441 -3.426662
H 2.362604 0.713444 -4.242550
H 1.724848 -0.681689 -3.355062
H 0.674576 0.696742 -3.718621
N -0.548087 -0.460360 -0.036131
N -2.034183 -0.602160 -0.163014
Si -2.581486 -0.351810 1.622856
Si -2.676183 0.689420 -1.383025
C -1.851695 2.352530 -1.146318
H -0.763210 2.263030 -1.159092
H -2.149448 2.979723 -1.996739
H -2.145741 2.871247 -0.233442
C -4.548159 0.884075 -1.187456
H -4.839379 1.342429 -0.238057
H -4.891381 1.555038 -1.985610
H -5.095946 -0.056002 -1.297720
C -2.348007 0.131737 -3.149235
H -2.638739 0.968246 -3.797606
H -1.293573 -0.076475 -3.336590
H -2.936677 -0.735250 -3.458871
C -4.328324 -1.050909 1.840680
H -5.053640 -0.647755 1.129484
H -4.359143 -2.142884 1.778128
H -4.672780 -0.779803 2.847027
C -2.620022 1.480960 2.031093
H -3.397206 2.043341 1.507633
41
H -2.830049 1.559684 3.105191
H -1.652397 1.952204 1.849476
C -1.463288 -1.182613 2.880590
H -1.826681 -0.875191 3.870691
H -1.485402 -2.272220 2.847724
H -0.431210 -0.846825 2.774356
C 3.424477 -3.232737 0.522192
C 4.262366 -2.459770 1.554047
C 3.635923 -1.059119 1.524820
O 2.282665 -1.230221 1.011811
C 2.040336 -2.630061 0.733843
H 3.775205 -3.027032 -0.495038
H 3.440283 -4.314979 0.679462
H 5.328087 -2.435062 1.311856
H 4.152830 -2.912547 2.545655
H 3.575151 -0.594999 2.513005
H 4.161816 -0.383134 0.847223
H 1.376249 -2.676473 -0.129367
H 1.535987 -3.082779 1.599213
Si -2.144685 -2.369969 -0.791637
C -1.758229 -3.609121 0.571701
H -2.507901 -3.641949 1.366238
H -1.756278 -4.596287 0.091022
H -0.774812 -3.451378 1.016590
C -3.917002 -2.745404 -1.353117
H -4.655319 -2.624489 -0.555023
H -4.241921 -2.149345 -2.210402
H -3.947354 -3.797519 -1.665812
C -0.961202 -2.654668 -2.225070
H -1.469599 -2.653584 -3.193198
H -0.171898 -1.901660 -2.229962
H -0.491111 -3.637066 -2.097938
--------------------------------------------------------
42
Supplementary Table S22 | Cartesian coordinate of TS between V and VI in the quartet state. Units are presented in Å.
SCF energy = -3651.113200 hartree
ZPE = 0.680831 hartree
Imaginary frequency: 461i
--------------------------------------------------------
Atom Coordinates (Angstroms)
X Y Z
--------------------------------------------------------
Fe 1.118373 0.391617 0.069673
Si 1.729424 2.217845 1.583698
C 3.556403 2.797949 1.522497
H 4.265833 1.982178 1.701607
H 3.812196 3.250362 0.558715
H 3.724993 3.555811 2.300025
C 1.466439 1.692088 3.411492
H 2.050334 0.800862 3.671706
H 1.777073 2.498878 4.089760
H 0.415641 1.465198 3.622009
C 0.718355 3.826379 1.369466
H 1.081030 4.581818 2.079716
H 0.819430 4.240558 0.361372
H -0.349180 3.679835 1.562740
Si 2.273678 1.266895 -1.906175
C 4.164286 0.966708 -1.796949
H 4.609551 1.415369 -0.903760
H 4.396640 -0.105043 -1.794712
H 4.659810 1.405357 -2.673964
C 2.062010 3.131709 -2.271062
H 2.462177 3.759861 -1.468261
H 2.597170 3.390621 -3.194909
H 1.010475 3.405816 -2.411610
C 1.775386 0.394005 -3.537686
H 2.423385 0.731037 -4.358726
H 1.870541 -0.695538 -3.466138
H 0.742256 0.619011 -3.822953
N -0.323493 -0.522344 0.085842
N -2.138733 -0.591444 -0.125797
Si -2.653810 -0.349803 1.630295
Si -2.668887 0.695282 -1.333109
C -1.821172 2.350557 -1.082557
H -0.733677 2.250669 -1.063179
H -2.084896 2.983781 -1.939534
H -2.132108 2.874608 -0.177986
C -4.541716 0.950002 -1.204267
H -4.857688 1.379160 -0.249023
H -4.843897 1.654320 -1.989990
H -5.102334 0.023515 -1.362017
C -2.320635 0.157641 -3.105361
H -2.627709 0.991856 -3.749085
H -1.261896 -0.029163 -3.293143
H -2.887831 -0.720120 -3.425148
C -4.396156 -1.057839 1.858460
H -5.120714 -0.644347 1.151223
H -4.425798 -2.148649 1.774116
H -4.741098 -0.805143 2.869309
C -2.725024 1.481906 2.060380
43
H -3.477270 2.047187 1.504471
H -2.990211 1.548576 3.122985
H -1.754970 1.965937 1.931591
C -1.536805 -1.154970 2.911896
H -1.896345 -0.829477 3.897340
H -1.560294 -2.245355 2.898077
H -0.504185 -0.825127 2.792902
C 3.411953 -3.356957 0.651304
C 4.259732 -2.497452 1.603193
C 3.751525 -1.075949 1.332656
O 2.410980 -1.229754 0.773653
C 2.068876 -2.639346 0.690469
H 3.824825 -3.335959 -0.363272
H 3.336467 -4.400473 0.969380
H 5.334081 -2.586925 1.422829
H 4.067624 -2.783507 2.642905
H 3.680269 -0.467496 2.237499
H 4.355110 -0.546697 0.591769
H 1.447397 -2.768952 -0.194803
H 1.486958 -2.912634 1.579513
Si -2.134229 -2.325280 -0.749627
C -1.770063 -3.583122 0.607362
H -2.534829 -3.623370 1.387432
H -1.757049 -4.566964 0.120275
H -0.797662 -3.423749 1.075514
C -3.879397 -2.752407 -1.364286
H -4.634220 -2.670151 -0.576325
H -4.207935 -2.138686 -2.208252
H -3.876859 -3.795361 -1.707382
C -0.928559 -2.617170 -2.172557
H -1.438083 -2.663433 -3.139613
H -0.156618 -1.848742 -2.213062
H -0.434891 -3.583815 -2.014812
--------------------------------------------------------
44
Supplementary Table S23 | Cartesian coordinate of VI-N(SiMe3)3 in the quartet state. Units are presented in Å.
SCF energy = -3651.316374 hartree
ZPE = 0.683227 hartree
--------------------------------------------------------
Atom Coordinates (Angstroms)
X Y Z
--------------------------------------------------------
Fe 3.256879 0.030510 -0.377115
Si 3.744991 2.975019 0.397684
C 5.185114 4.149109 -0.000010
H 6.117747 3.591551 -0.144997
H 5.008454 4.740893 -0.905001
H 5.343273 4.854509 0.825511
C 4.193834 2.128134 2.037447
H 5.089270 1.503971 1.935947
H 4.399250 2.883844 2.807531
H 3.379230 1.493656 2.405794
C 2.208099 4.034421 0.736107
H 2.382533 4.731517 1.565552
H 1.921580 4.624775 -0.140777
H 1.352791 3.402554 1.002547
Si 3.445043 2.156059 -2.590489
C 5.188960 2.143395 -3.336868
H 5.830035 2.899389 -2.869599
H 5.666197 1.168025 -3.185888
H 5.165378 2.344227 -4.415554
C 2.664576 3.843588 -2.981353
H 3.202470 4.677104 -2.516819
H 2.668711 4.016966 -4.064882
H 1.623392 3.887911 -2.642216
C 2.418967 0.873438 -3.543159
H 2.380643 1.131983 -4.609748
H 2.844607 -0.133718 -3.462441
H 1.389047 0.834205 -3.170015
N 3.471344 1.817784 -0.878583
N -3.660255 -1.095182 -0.339798
Si -3.911792 -1.250878 1.416288
Si -3.866861 0.496023 -1.123886
C -2.682897 1.796528 -0.432011
H -1.659396 1.407777 -0.380545
H -2.668946 2.659404 -1.109314
H -2.954735 2.165810 0.558732
C -5.660876 1.082622 -0.966284
H -6.004369 1.160800 0.069516
H -5.780854 2.070555 -1.427729
H -6.335351 0.391093 -1.484760
C -3.496151 0.464268 -2.981148
H -3.797571 1.443580 -3.374392
H -2.428578 0.350307 -3.190212
H -4.042582 -0.291057 -3.552052
C -5.529425 -2.164099 1.786795
H -6.383853 -1.580961 1.423567
H -5.590009 -3.154507 1.325960
H -5.655162 -2.295264 2.868711
C -4.040105 0.409054 2.318571
H -4.777392 1.104692 1.910244
45
H -4.348741 0.180443 3.346796
H -3.077514 0.925060 2.377231
C -2.460000 -2.116951 2.272518
H -2.550854 -1.978030 3.356956
H -2.403741 -3.190699 2.082998
H -1.511658 -1.661933 1.962955
C 2.172329 -4.080891 0.347197
C 3.394142 -3.946286 1.269734
C 4.108217 -2.722136 0.703991
O 3.035301 -1.881380 0.161748
C 1.773867 -2.627988 0.105377
H 2.452580 -4.563464 -0.595090
H 1.358360 -4.655097 0.796292
H 4.036606 -4.830231 1.261235
H 3.077872 -3.762788 2.301997
H 4.648145 -2.132179 1.446394
H 4.781053 -2.973433 -0.122060
H 1.321672 -2.441402 -0.869992
H 1.121165 -2.236526 0.891937
Si -3.500522 -2.555680 -1.343380
C -3.205513 -4.133723 -0.333006
H -3.934321 -4.325809 0.458606
H -3.267833 -4.972062 -1.038700
H -2.205245 -4.158932 0.110133
C -5.075411 -2.869707 -2.345091
H -5.918109 -3.086068 -1.678247
H -5.362847 -2.020440 -2.972255
H -4.943336 -3.736587 -3.004348
C -2.001360 -2.475892 -2.498917
H -2.160219 -1.871815 -3.394592
H -1.128108 -2.070502 -1.974824
H -1.750067 -3.491529 -2.829274
--------------------------------------------------------
46
Supplementary Table S24 | Cartesian coordinate of VII in the quartet state. Units are presented in Å.
SCF energy = -2778.191802 hartree
ZPE = 0.453264 hartree
--------------------------------------------------------
Atom Coordinates (Angstroms)
X Y Z
--------------------------------------------------------
Fe 4.062061 1.277161 0.351975
Si 1.396582 2.139061 1.794823
C 2.646924 2.164947 3.221684
H 3.127924 1.191258 3.376597
H 3.438252 2.905652 3.061835
H 2.136165 2.425463 4.157671
C 0.074024 0.856070 2.253410
H 0.507136 -0.147800 2.339360
H -0.385719 1.100862 3.219203
H -0.726109 0.808365 1.507540
C 0.562342 3.840984 1.753486
H 0.108168 4.071986 2.725088
H 1.289503 4.629535 1.529089
H -0.232034 3.897405 1.000713
Si 1.501958 1.940360 -1.305823
C 2.394692 0.812486 -2.546842
H 3.458055 1.062343 -2.641999
H 2.320008 -0.244527 -2.263819
H 1.945891 0.916773 -3.542745
C 1.659087 3.716194 -1.944224
H 2.709371 4.026801 -1.983772
H 1.243142 3.811081 -2.955135
H 1.129209 4.424641 -1.297982
C -0.335057 1.465611 -1.370797
H -0.713288 1.582566 -2.394178
H -0.497387 0.422689 -1.075528
H -0.954563 2.095472 -0.722857
N 2.191927 1.745216 0.289342
C 3.666821 -3.130570 0.346292
C 5.174005 -3.019910 0.630118
C 5.487634 -1.590408 0.198699
O 4.259752 -0.837218 0.462483
C 3.153909 -1.753134 0.753596
H 3.488663 -3.307060 -0.719994
H 3.181717 -3.931466 0.910138
H 5.770064 -3.752743 0.080351
H 5.373750 -3.150854 1.699161
H 6.297776 -1.117798 0.756952
H 5.700032 -1.520643 -0.873521
H 2.283162 -1.403001 0.197849
H 2.943260 -1.692518 1.826832
Si 6.135134 2.684282 0.242567
C 6.319326 3.591265 -1.432376
H 5.456800 4.236270 -1.636091
H 7.216549 4.225215 -1.435243
H 6.406591 2.886698 -2.267744
C 6.146601 4.054528 1.577623
H 5.274276 4.711633 1.483474
H 6.136107 3.635383 2.590423
47
H 7.045391 4.679128 1.484474
C 7.777926 1.720595 0.483785
H 7.812897 1.216907 1.457557
H 7.919348 0.958757 -0.292570
H 8.638414 2.401938 0.435264
--------------------------------------------------------
48
Supplementary Table S25 | Cartesian coordinate of VII-SiMe3 in the quartet state. Units are presented in Å.
SCF energy = -3187.29308774 hartree
ZPE = 0.562351 hartree
--------------------------------------------------------
Atom Coordinates (Angstroms)
X Y Z
--------------------------------------------------------
Fe 0.332258 0.351448 -0.446358
Si 1.698627 0.792910 2.348723
C 2.843854 -0.483520 1.536300
H 2.318671 -1.413000 1.284549
H 3.308165 -0.103445 0.619526
H 3.653077 -0.746874 2.229599
C 1.022222 -0.019661 3.926499
H 0.423110 -0.908028 3.691502
H 1.843249 -0.340755 4.579943
H 0.388632 0.663850 4.501070
C 2.779093 2.260094 2.872601
H 3.587725 1.928492 3.535833
H 3.238592 2.740859 2.001581
H 2.208205 3.024756 3.411393
Si 1.411986 0.827604 -2.661553
C 0.620862 -0.093863 -4.148861
H 0.715094 -1.182222 -4.050587
H -0.445867 0.140641 -4.248893
H 1.112231 0.194308 -5.088304
C 3.267294 0.356125 -2.707913
H 3.422153 -0.711376 -2.511829
H 3.700585 0.580384 -3.692269
H 3.842480 0.913785 -1.959637
C 1.340884 2.682712 -3.123132
H 1.840540 2.862029 -4.084939
H 0.308055 3.038947 -3.212511
H 1.838736 3.303184 -2.369201
N 0.419596 1.258943 1.253663
Si -0.641058 2.634671 1.455365
C -1.168100 2.893709 3.260696
H -1.687565 2.015977 3.661670
H -0.319812 3.109517 3.919901
H -1.856033 3.745869 3.328481
C -2.237268 2.379796 0.458195
H -2.783260 1.489339 0.792026
H -2.904407 3.241425 0.586168
H -2.041936 2.274964 -0.615643
C 0.158938 4.241251 0.851679
H 0.435686 4.167167 -0.206135
H -0.523139 5.093659 0.961740
H 1.070265 4.468326 1.416026
C -2.065479 -3.384071 -0.819571
C -1.991617 -3.194051 0.704682
C -1.771114 -1.692236 0.832253
O -0.945957 -1.341226 -0.323408
C -1.023582 -2.394721 -1.340682
H -1.847922 -4.407630 -1.135344
H -3.059795 -3.115498 -1.192719
H -1.141407 -3.742860 1.124391
49
H -2.898210 -3.521617 1.220309
H -2.710939 -1.133084 0.761491
H -1.230622 -1.376259 1.725481
H -0.027520 -2.840177 -1.427134
H -1.296057 -1.928063 -2.289415
Si -4.954331 -0.919685 -3.485245
C -4.494004 0.916556 -3.508699
H -3.503127 1.074042 -3.946816
H -5.219021 1.485631 -4.107920
H -4.486660 1.342558 -2.500238
C -4.891441 -1.653731 -5.230892
H -3.901543 -1.526163 -5.680912
H -5.124581 -2.723592 -5.225737
H -5.622031 -1.155246 -5.883752
C -6.665515 -1.175627 -2.710757
H -7.436169 -0.661912 -3.302890
H -6.931725 -2.236896 -2.667447
H -6.707009 -0.774889 -1.692590
--------------------------------------------------------
50
Supplementary Table S26 | Cartesian coordinate of TS between VII-SiMe3 and VIII in the quartet state. Units are presented in Å.
SCF energy = -3187.29206970 hartree
ZPE = 0.562280 hartree
Imaginary frequency: 18i
--------------------------------------------------------
Atom Coordinates (Angstroms)
X Y Z
--------------------------------------------------------
Fe -0.081300 0.213223 -0.609668
Si 1.445558 0.636468 2.113988
C 2.507417 -0.689694 1.268492
H 1.935992 -1.597287 1.038652
H 2.952540 -0.329193 0.334912
H 3.329202 -0.983058 1.934465
C 0.852141 -0.124286 3.751160
H 0.241487 -1.019553 3.580263
H 1.709069 -0.426507 4.366578
H 0.252262 0.577059 4.339901
C 2.595921 2.082726 2.537987
H 3.428277 1.742208 3.166432
H 3.022605 2.525865 1.631020
H 2.078617 2.878914 3.084922
Si 1.011629 0.720715 -2.808969
C 0.756172 -0.585649 -4.190502
H 1.133290 -1.571220 -3.892029
H -0.303439 -0.699481 -4.449117
H 1.291282 -0.291419 -5.103936
C 2.908842 0.884690 -2.612073
H 3.367967 -0.055321 -2.284653
H 3.373264 1.166492 -3.567024
H 3.170521 1.653826 -1.876244
C 0.438523 2.382683 -3.565783
H 0.974775 2.585886 -4.502851
H -0.634498 2.380926 -3.787753
H 0.631530 3.220822 -2.886233
N 0.113360 1.114260 1.088925
Si -0.905781 2.512266 1.346594
C -1.300667 2.811388 3.179058
H -1.806924 1.951287 3.631518
H -0.405015 3.022808 3.773485
H -1.966857 3.677746 3.277226
C -2.571256 2.276826 0.465865
H -3.112211 1.405109 0.853314
H -3.210025 3.155982 0.618083
H -2.447182 2.143814 -0.615633
C -0.123124 4.095684 0.662330
H 0.060382 4.007146 -0.414537
H -0.774725 4.964216 0.820577
H 0.838036 4.307429 1.143815
C -2.117324 -3.755063 -0.651084
C -1.991336 -3.486033 0.858001
C -1.876153 -1.967562 0.905291
O -1.127885 -1.619018 -0.300009
C -1.174345 -2.718886 -1.264340
H -1.840131 -4.774622 -0.930588
H -3.146443 -3.580478 -0.982966
51
H -1.084820 -3.951402 1.260017
H -2.847011 -3.852936 1.430943
H -2.857027 -1.480897 0.852962
H -1.323732 -1.569550 1.757174
H -0.154017 -3.097693 -1.380005
H -1.520255 -2.311824 -2.217412
Si -3.822291 -0.002238 -3.158488
C -3.907254 1.771301 -3.812484
H -3.105510 1.971742 -4.530145
H -4.865845 1.942598 -4.322761
H -3.824071 2.502256 -3.002116
C -3.946307 -1.240348 -4.591446
H -3.134437 -1.098572 -5.312162
H -3.906176 -2.276695 -4.239325
H -4.896411 -1.108881 -5.128870
C -5.208229 -0.311131 -1.899774
H -6.191495 -0.162871 -2.368574
H -5.179957 -1.333296 -1.507108
H -5.134152 0.379844 -1.053879
--------------------------------------------------------
52
Supplementary Table S27 | Cartesian coordinate of VIII in the quartet state. Units are presented in Å.
SCF energy = -3187.33224272 hartree
ZPE = 0.565976 hartree
--------------------------------------------------------
Atom Coordinates (Angstroms)
X Y Z
--------------------------------------------------------
Fe 3.728728 2.480158 0.313528
Si 1.179854 2.292317 2.121988
C 2.119380 3.556389 3.175730
H 3.191088 3.350591 3.250820
H 2.001881 4.570901 2.780535
H 1.714791 3.549940 4.195909
C 1.310620 0.607163 2.989320
H 2.349269 0.260013 3.039870
H 0.929273 0.657489 4.016957
H 0.730810 -0.156608 2.458137
C -0.641254 2.823735 2.234491
H -0.936575 2.850080 3.291224
H -0.798303 3.827741 1.825233
H -1.328933 2.141461 1.724337
Si 0.786418 1.788140 -0.869149
C 1.781005 1.441735 -2.448556
H 2.452091 2.264126 -2.713701
H 2.375361 0.526739 -2.366817
H 1.084254 1.305451 -3.285143
C -0.447201 3.159729 -1.313805
H 0.060270 4.112229 -1.502712
H -1.000937 2.893320 -2.223015
H -1.179135 3.328854 -0.518580
C -0.223742 0.204587 -0.560911
H -0.829806 -0.035779 -1.443653
H 0.425997 -0.656882 -0.364131
H -0.908739 0.298023 0.288345
N 1.810215 2.199026 0.487406
C 4.384691 -1.651938 -1.327388
C 5.638569 -0.978652 -1.909683
C 5.303596 0.505135 -1.776389
O 4.465087 0.603398 -0.587648
C 4.019956 -0.722914 -0.171939
H 3.581638 -1.673890 -2.071596
H 4.563962 -2.675918 -0.989553
H 5.836920 -1.263052 -2.946348
H 6.521839 -1.229253 -1.311800
H 6.173627 1.146951 -1.626259
H 4.725283 0.871983 -2.631347
H 2.951586 -0.660396 0.042755
H 4.554401 -0.988590 0.747228
Si 5.811230 2.674688 1.647936
C 7.436302 2.197279 0.766912
H 7.724911 2.902135 -0.018219
H 8.251014 2.169844 1.502852
H 7.369409 1.198783 0.320879
C 6.184386 4.217816 2.698407
H 6.488208 5.079497 2.097052
H 5.321335 4.518961 3.300794
53
H 7.006904 3.989469 3.389201
C 5.515474 1.268420 2.919758
H 4.658357 1.460455 3.572828
H 5.361194 0.295885 2.440748
H 6.404952 1.180392 3.559116
Si 4.301606 4.703873 -0.508178
C 3.293790 4.914800 -2.116530
H 2.225391 4.742586 -1.963694
H 3.421969 5.946820 -2.471863
H 3.637240 4.247406 -2.913898
C 3.714922 6.089336 0.654879
H 2.637856 6.014774 0.836670
H 4.221561 6.081144 1.623436
H 3.906354 7.062451 0.182889
C 6.090218 5.098500 -1.036218
H 6.792846 5.156642 -0.200720
H 6.472665 4.358405 -1.747758
H 6.095958 6.073248 -1.542319
--------------------------------------------------------
54
Supplementary Table S28 | Cartesian coordinate of TS between VIII and IX in the quartet state. Units are presented in Å.
SCF energy = -3187.30179163 hartree
ZPE = 0.565851 hartree
Imaginary frequency: 150i
--------------------------------------------------------
Atom Coordinates (Angstroms)
X Y Z
--------------------------------------------------------
Fe 3.940037 2.242149 0.364184
Si 1.420899 2.898344 1.972427
C 2.469636 3.981309 3.112869
H 3.507411 3.642098 3.173255
H 2.473022 5.039890 2.840458
H 2.039994 3.908891 4.120609
C 1.428889 1.177433 2.766387
H 2.449577 0.780418 2.818957
H 1.049682 1.242325 3.794406
H 0.810000 0.451784 2.232108
C -0.346921 3.577299 2.048139
H -0.677528 3.585910 3.094352
H -0.398654 4.605922 1.677228
H -1.070626 2.980252 1.485316
Si 0.987927 2.206615 -1.008349
C 1.941190 1.515764 -2.488137
H 2.665122 2.210857 -2.918782
H 2.470822 0.600281 -2.213888
H 1.216416 1.265492 -3.273631
C -0.223966 3.494564 -1.686984
H 0.277479 4.292820 -2.243035
H -0.909480 2.994970 -2.383367
H -0.831509 3.958506 -0.904031
C -0.068325 0.749136 -0.404288
H -0.674446 0.399464 -1.250012
H 0.547062 -0.094526 -0.074609
H -0.758987 0.999097 0.405978
N 2.047608 2.852111 0.285432
C 4.294233 -2.241409 -0.757359
C 5.543251 -1.655361 -1.435822
C 5.174789 -0.179027 -1.606643
O 4.196715 0.115020 -0.566688
C 3.861904 -1.099223 0.157718
H 3.515447 -2.454355 -1.498092
H 4.499003 -3.161192 -0.202940
H 5.776977 -2.132697 -2.391049
H 6.414880 -1.760705 -0.781813
H 6.022406 0.499296 -1.481348
H 4.700571 0.019386 -2.574471
H 2.789025 -1.079590 0.364603
H 4.411351 -1.106581 1.106187
Si 6.233378 2.265547 1.364515
C 7.653953 2.788472 0.179349
H 7.545689 3.822722 -0.166564
H 8.625406 2.711319 0.686818
H 7.700004 2.153115 -0.713976
C 6.502228 3.319825 2.943296
H 6.331154 4.386686 2.769153
55
H 5.836077 3.005382 3.755766
H 7.533933 3.202389 3.302416
C 6.756793 0.501864 1.939665
H 6.071744 0.098207 2.695556
H 6.796496 -0.214155 1.110464
H 7.758045 0.533260 2.390959
Si 3.301243 4.636862 -0.240442
C 3.631107 4.640680 -2.114014
H 2.745550 4.402615 -2.708608
H 3.935781 5.662798 -2.377111
H 4.440782 3.967267 -2.409593
C 1.863412 5.860443 0.015126
H 0.926811 5.548819 -0.448615
H 1.666038 6.065668 1.071475
H 2.165512 6.813268 -0.440340
C 4.736900 5.606220 0.567962
H 4.664310 5.629409 1.658503
H 5.711221 5.190904 0.302161
H 4.687436 6.644818 0.209455
--------------------------------------------------------
56
Supplementary Table S29 | Cartesian coordinate of IX in the quartet state. Units are presented in Å.
SCF energy = -3187.32035305 hartree
ZPE = 0.566276 hartree
--------------------------------------------------------
Atom Coordinates (Angstroms)
X Y Z
--------------------------------------------------------
Fe 0.917476 0.564365 0.157574
Si -1.940644 0.551579 1.470202
C -1.517969 1.466209 3.067252
H -0.448145 1.433093 3.291908
H -1.852936 2.505916 3.104239
H -2.037812 0.931247 3.873040
C -1.410574 -1.232793 1.770567
H -0.385638 -1.266233 2.156125
H -2.068043 -1.655348 2.543243
H -1.453965 -1.886858 0.898249
C -3.822944 0.650239 1.293242
H -4.273184 0.247434 2.209325
H -4.169395 1.683193 1.187480
H -4.224450 0.073441 0.456222
Si -1.712886 0.637223 -1.631291
C -0.372410 0.625522 -2.959821
H 0.094069 1.593800 -3.147229
H 0.421664 -0.088255 -2.719012
H -0.842589 0.295953 -3.896846
C -3.167399 1.678961 -2.250835
H -2.903500 2.715473 -2.478283
H -3.532841 1.226641 -3.181262
H -4.002116 1.689504 -1.543137
C -2.320760 -1.142860 -1.526233
H -2.712261 -1.381105 -2.524703
H -1.528268 -1.867198 -1.314309
H -3.136176 -1.308803 -0.818078
N -1.106185 1.278759 -0.004401
C 0.830084 -5.916996 -0.329445
C 1.823953 -4.776831 -0.054761
C 1.228639 -3.644082 -0.889431
O -0.199823 -3.817702 -0.816491
C -0.508603 -5.169863 -0.420706
H 1.065265 -6.402586 -1.283333
H 0.826267 -6.685812 0.448168
H 2.851004 -5.018446 -0.341636
H 1.819872 -4.508576 1.007734
H 1.465372 -2.642953 -0.516035
H 1.552874 -3.713452 -1.938955
H -1.192738 -5.607984 -1.156339
H -1.020094 -5.137233 0.550704
Si 3.324531 0.136750 0.431354
C 4.200895 -0.461057 -1.166553
H 4.088262 0.267888 -1.977779
H 5.276389 -0.606775 -0.994770
H 3.788465 -1.412156 -1.524006
C 4.283324 1.713856 0.958526
H 4.173039 2.516955 0.219989
H 3.926038 2.100344 1.920659
57
H 5.356897 1.504036 1.063349
C 3.759187 -1.169807 1.767178
H 3.373629 -0.877495 2.751088
H 3.334797 -2.152207 1.528767
H 4.847642 -1.290625 1.857550
Si -0.819944 3.102485 0.058025
C -0.156700 3.765609 -1.580763
H -0.817182 3.618520 -2.438473
H -0.029349 4.848104 -1.450698
H 0.825568 3.348511 -1.822165
C -2.443013 4.008918 0.421644
H -3.219634 3.806562 -0.321402
H -2.851981 3.774182 1.409064
H -2.244741 5.088051 0.405427
C 0.433645 3.652122 1.358321
H 0.141795 3.431116 2.385828
H 1.425330 3.223608 1.185718
H 0.523363 4.743918 1.269144
--------------------------------------------------------
58
Supplementary Table S30 | Cartesian coordinate of IX-SiMe3 in the quintet state. Units are presented in Å.
SCF energy = -3596.42086689 hartree
ZPE = 0.675342 hartree
--------------------------------------------------------
Atom Coordinates (Angstroms)
X Y Z
--------------------------------------------------------
Fe 0.832847 0.452879 0.290545
Si -1.992463 0.452574 1.667632
C -1.544839 1.460384 3.200707
H -0.469698 1.449104 3.401700
H -1.888434 2.497755 3.186719
H -2.040607 0.967389 4.047388
C -1.424877 -1.303167 2.054173
H -0.370384 -1.310368 2.350682
H -2.012413 -1.666832 2.908638
H -1.544039 -2.016104 1.237223
C -3.880355 0.500691 1.534567
H -4.298608 0.122485 2.475971
H -4.254696 1.520081 1.397975
H -4.286338 -0.117702 0.729789
Si -1.834631 0.360272 -1.439264
C -0.525219 0.313328 -2.796751
H -0.090400 1.280196 -3.055122
H 0.293918 -0.363411 -2.533463
H -1.006974 -0.086734 -3.699977
C -3.341999 1.312851 -2.077857
H -3.127317 2.346713 -2.361755
H -3.706025 0.799908 -2.976909
H -4.163071 1.324667 -1.354287
C -2.378361 -1.430787 -1.222260
H -2.783301 -1.734302 -2.197451
H -1.552399 -2.112882 -0.997834
H -3.171149 -1.586982 -0.486726
N -1.210551 1.110800 0.134187
C 0.359271 -6.092811 0.345802
C 1.482991 -5.062239 0.648150
C 1.258225 -3.965366 -0.406566
O -0.136973 -4.029775 -0.721602
C -0.457053 -5.422004 -0.780997
H 0.756647 -7.060463 0.026438
H -0.259642 -6.265497 1.230322
H 2.484161 -5.496124 0.578080
H 1.368753 -4.650701 1.654630
H 1.474212 -2.952516 -0.058679
H 1.852147 -4.161579 -1.314016
H -0.170788 -5.825287 -1.765575
H -1.539419 -5.519305 -0.666493
Si 3.242941 0.040227 0.551999
C 4.099784 -0.600964 -1.039863
H 3.973440 0.106624 -1.867857
H 5.177829 -0.740315 -0.878828
H 3.683556 -1.561530 -1.366145
C 4.205953 1.632297 1.023029
H 4.090652 2.412101 0.260691
H 3.854564 2.048602 1.974786
59
H 5.280235 1.425447 1.127242
C 3.697752 -1.227220 1.918834
H 3.333410 -0.902199 2.900613
H 3.264408 -2.214613 1.720523
H 4.787188 -1.351074 1.991521
Si -0.983324 2.944008 0.083620
C -0.403640 3.535370 -1.611558
H -1.088682 3.322364 -2.435443
H -0.308185 4.626906 -1.543421
H 0.582442 3.139281 -1.870873
C -2.623734 3.814519 0.456707
H -3.422291 3.526005 -0.232535
H -2.979666 3.642362 1.476857
H -2.469702 4.895559 0.348600
C 0.298240 3.607132 1.301014
H 0.092196 3.380558 2.347769
H 1.306008 3.250805 1.068663
H 0.299580 4.701306 1.195299
Si 2.957205 3.058568 -5.411484
C 4.602118 3.821560 -4.860265
H 5.291310 3.910348 -5.712285
H 4.458138 4.823003 -4.441442
H 5.090497 3.206012 -4.097889
C 2.103278 4.170705 -6.689534
H 2.721881 4.267079 -7.593301
H 1.133835 3.759953 -6.990672
H 1.933042 5.177058 -6.292858
C 3.232982 1.323896 -6.123672
H 3.893603 1.367973 -7.001453
H 3.698125 0.660199 -5.387674
H 2.289131 0.866791 -6.438532
--------------------------------------------------------
60
Supplementary Table S31 | Cartesian coordinate of TS between IX-SiMe3 and X in the quintet state. Units are presented in Å.
SCF energy = -3596.42043599 hartree
ZPE = 0.675455 hartree
Imaginary frequency: 41i
--------------------------------------------------------
Atom Coordinates (Angstroms)
X Y Z
--------------------------------------------------------
Fe 0.938867 0.777206 -0.356659
Si -1.602676 0.581841 1.412526
C -0.982412 1.659590 2.834184
H 0.106654 1.759943 2.833897
H -1.427725 2.656634 2.883816
H -1.260904 1.135651 3.758067
C -0.865675 -1.124989 1.722027
H 0.197652 -1.048147 1.968417
H -1.378052 -1.548601 2.597725
H -0.964378 -1.838922 0.903340
C -3.486130 0.486749 1.605226
H -3.707455 0.127482 2.618205
H -3.963000 1.464938 1.493932
H -3.967632 -0.203341 0.907046
Si -1.979892 0.430605 -1.664903
C -0.889834 0.465802 -3.202056
H -0.643889 1.467048 -3.558367
H 0.052184 -0.067952 -3.035942
H -1.428241 -0.056716 -4.004396
C -3.652789 1.224392 -2.062296
H -3.591901 2.268440 -2.380447
H -4.105308 0.660243 -2.887566
H -4.342382 1.168374 -1.214040
C -2.326639 -1.392286 -1.340628
H -2.857638 -1.751506 -2.232924
H -1.424583 -2.002565 -1.239342
H -2.975181 -1.592151 -0.484244
N -1.168593 1.283493 -0.241969
C 0.655730 -6.000334 0.175151
C 1.887531 -5.067641 0.005440
C 1.386837 -3.983676 -0.965120
O -0.032245 -3.939645 -0.781615
C -0.448043 -5.301167 -0.647709
H 0.845466 -7.012747 -0.192603
H 0.369644 -6.079170 1.227339
H 2.762897 -5.591750 -0.387804
H 2.169742 -4.621612 0.962828
H 1.778761 -2.984317 -0.765189
H 1.617046 -4.251763 -2.009161
H -0.542900 -5.758947 -1.645522
H -1.430236 -5.303452 -0.168946
Si 3.239060 0.171962 0.274316
C 4.294907 -0.632191 -1.108710
H 4.413461 0.046565 -1.960479
H 5.298347 -0.885289 -0.739596
H 3.836434 -1.553075 -1.488058
C 4.269558 1.669313 0.886786
H 4.376216 2.436023 0.110850
61
H 3.801800 2.147135 1.755941
H 5.278567 1.352105 1.184948
C 3.304424 -1.075401 1.733999
H 2.835104 -0.662504 2.635239
H 2.789603 -2.014268 1.498292
H 4.345273 -1.320767 1.987053
Si -1.169452 3.127039 -0.332888
C -0.956271 3.735831 -2.106440
H -1.744908 3.434035 -2.799595
H -0.966458 4.832682 -2.061358
H 0.009694 3.437201 -2.527422
C -2.795906 3.836455 0.325554
H -3.673678 3.446332 -0.197346
H -2.936223 3.666357 1.397092
H -2.777426 4.922890 0.172230
C 0.239977 3.937772 0.626140
H 0.233416 3.738112 1.698444
H 1.220272 3.649132 0.235037
H 0.134126 5.023457 0.491876
Si 2.773124 2.494248 -4.129325
C 4.418496 3.195420 -3.497119
H 5.110624 3.367822 -4.333964
H 4.273361 4.150252 -2.980820
H 4.902613 2.506954 -2.797317
C 1.955903 3.746561 -5.304875
H 2.614377 3.954852 -6.160647
H 1.007809 3.366464 -5.700154
H 1.752608 4.698068 -4.802167
C 3.066236 0.862498 -5.052444
H 3.752484 1.016694 -5.897685
H 3.506263 0.105390 -4.395837
H 2.129748 0.458680 -5.451357
--------------------------------------------------------
62
Supplementary Table S32 | Cartesian coordinate of X in the quintet state. Units are presented in Å.
SCF energy = -3596.46019999 hartree
ZPE = 0.677560 hartree
--------------------------------------------------------
Atom Coordinates (Angstroms)
X Y Z
--------------------------------------------------------
Fe 0.611897 0.822864 0.160512
Si -2.136556 -0.219299 1.801673
C -1.746719 0.869185 3.291880
H -0.697602 1.171368 3.328172
H -2.373025 1.761620 3.369657
H -1.938598 0.261117 4.184941
C -1.148047 -1.817644 1.987427
H -0.151030 -1.773157 1.541441
H -1.017588 -2.008420 3.059070
H -1.668645 -2.677335 1.560816
C -3.967859 -0.683096 1.937764
H -4.112148 -1.179501 2.906171
H -4.635621 0.182150 1.911444
H -4.293819 -1.386883 1.166786
Si -2.315128 -0.275330 -1.263543
C -1.267225 0.094992 -2.780299
H -1.216748 1.146696 -3.060152
H -0.242727 -0.269220 -2.656463
H -1.712271 -0.453716 -3.620955
C -4.128065 0.107168 -1.661232
H -4.319992 1.147937 -1.934875
H -4.420552 -0.510879 -2.519531
H -4.795292 -0.151827 -0.833520
C -2.211766 -2.144331 -1.048330
H -2.509832 -2.562442 -2.019397
H -1.206639 -2.521685 -0.839341
H -2.901277 -2.554477 -0.306361
N -1.758889 0.656271 0.227953
C 2.792966 -5.253813 -0.615256
C 2.956364 -4.395133 -1.899890
C 1.506419 -4.097901 -2.317160
O 0.747919 -4.143066 -1.106256
C 1.268500 -5.250613 -0.364483
H 3.171310 -6.271853 -0.744732
H 3.329625 -4.801772 0.222227
H 3.510304 -4.913449 -2.687656
H 3.484460 -3.465336 -1.673710
H 1.363626 -3.111338 -2.764175
H 1.132906 -4.861404 -3.019724
H 0.808536 -6.184633 -0.725373
H 0.990030 -5.107963 0.682312
Si 2.287188 0.026793 1.899813
C 3.060983 -1.640625 1.356314
H 3.530619 -1.557530 0.369768
H 3.833783 -1.956484 2.070642
H 2.311477 -2.437790 1.295869
C 3.752226 1.252454 2.033925
H 4.256670 1.413528 1.076302
H 3.425010 2.231382 2.403105
63
H 4.497962 0.863912 2.741105
C 1.774721 -0.237081 3.730556
H 1.425832 0.691751 4.196519
H 0.988498 -0.988653 3.851489
H 2.649512 -0.578584 4.301119
Si 2.025902 1.990299 -1.605184
C 1.382931 2.503841 -3.339524
H 0.564820 3.231746 -3.296903
H 2.206641 2.976650 -3.892170
H 1.039525 1.648149 -3.929808
C 2.734228 3.619248 -0.884284
H 1.949288 4.375347 -0.759829
H 3.209210 3.472936 0.090860
H 3.488510 4.039225 -1.563931
C 3.531200 0.874561 -2.010779
H 4.080478 0.565535 -1.115901
H 3.216585 -0.035635 -2.535404
H 4.232781 1.408575 -2.666123
Si -2.198518 2.443284 0.220137
C -3.932540 2.754773 0.909206
H -4.032534 2.509464 1.970259
H -4.146115 3.826174 0.805949
H -4.708395 2.212767 0.360650
C -2.153047 3.180553 -1.515519
H -2.863758 2.747319 -2.222387
H -2.409075 4.242521 -1.408561
H -1.154964 3.131919 -1.956938
C -0.977970 3.479088 1.221737
H 0.042599 3.425064 0.826831
H -1.299968 4.525617 1.135106
H -0.941805 3.233566 2.284084
--------------------------------------------------------
64
Supplementary Table S33 | Cartesian coordinate of TS between X and I-N(SiMe3)3 in the quintet state. Units are presented in Å.
SCF energy = -3596.45963681 hartree
ZPE = 0.677680 hartree
Imaginary frequency: 46i
--------------------------------------------------------
Atom Coordinates (Angstroms)
X Y Z
--------------------------------------------------------
Fe 1.184505 0.617485 -0.944983
Si -1.200320 0.761864 1.485349
C -0.193956 1.931131 2.573015
H 0.867353 1.945551 2.315038
H -0.563793 2.959454 2.580602
H -0.275630 1.551777 3.599585
C -0.548385 -0.982833 1.785967
H 0.342070 -1.208850 1.193455
H -0.260531 -1.058202 2.841078
H -1.296635 -1.752774 1.589249
C -2.974021 0.831121 2.147319
H -2.946336 0.555278 3.209385
H -3.411586 1.831270 2.080354
H -3.652387 0.130772 1.652236
Si -2.282419 0.310052 -1.352008
C -1.667910 0.147749 -3.122511
H -1.537348 1.094006 -3.646991
H -0.719341 -0.394389 -3.168751
H -2.412480 -0.440143 -3.675119
C -3.990091 1.130438 -1.377476
H -4.000144 2.125653 -1.829930
H -4.657576 0.497963 -1.976565
H -4.428918 1.210953 -0.378405
C -2.551127 -1.463631 -0.769053
H -3.204342 -1.928397 -1.519427
H -1.617792 -2.033530 -0.744354
H -3.056843 -1.557299 0.194899
N -1.104800 1.230646 -0.285653
C 1.346219 -4.435712 -2.891328
C 1.522829 -4.831821 -1.417216
C 1.480668 -3.470102 -0.721969
O 0.589332 -2.648284 -1.508196
C 0.359136 -3.269335 -2.791995
H 2.298973 -4.094651 -3.310827
H 0.969236 -5.248895 -3.517699
H 2.453497 -5.371947 -1.222856
H 0.687619 -5.459431 -1.085433
H 1.093342 -3.511787 0.300474
H 2.472842 -3.001176 -0.701072
H 0.502239 -2.517034 -3.573531
H -0.682181 -3.618914 -2.831259
Si 3.118322 0.448661 0.703762
C 4.582586 -0.470853 -0.124832
H 4.920062 0.021688 -1.041918
H 5.435784 -0.506660 0.566408
H 4.321935 -1.503949 -0.382616
C 3.834602 2.165124 1.174884
H 4.061482 2.771652 0.290952
65
H 3.146678 2.744734 1.801354
H 4.768117 2.042295 1.741048
C 2.926480 -0.462994 2.383215
H 2.186591 0.004631 3.040848
H 2.635431 -1.511041 2.250020
H 3.890389 -0.452333 2.910341
Si -1.058997 3.040303 -0.599293
C -1.331556 3.472962 -2.416179
H -2.301264 3.177265 -2.822916
H -1.278172 4.567747 -2.476562
H -0.547795 3.075256 -3.064614
C -2.412116 3.949812 0.366556
H -3.415220 3.588486 0.121145
H -2.290771 3.899028 1.452270
H -2.369042 5.010393 0.087979
C 0.596061 3.826876 -0.152511
H 0.852509 3.774806 0.906126
H 1.429305 3.406042 -0.724192
H 0.525931 4.889526 -0.421175
Si 2.288773 0.977528 -3.201663
C 3.620396 2.342720 -2.988059
H 4.187156 2.465782 -3.921273
H 3.171044 3.313725 -2.746968
H 4.337632 2.107145 -2.194967
C 1.329242 1.524597 -4.771574
H 2.036308 1.613617 -5.607941
H 0.558089 0.805490 -5.066441
H 0.847572 2.501193 -4.651369
C 3.241732 -0.580365 -3.788599
H 3.880433 -0.329693 -4.646803
H 3.883031 -0.998658 -3.006559
H 2.554540 -1.370717 -4.113368
--------------------------------------------------------
66
Supplementary Table S34 | Cartesian coordinate of I-N(SiMe3)3 in the quintet state. Units are presented in Å.
SCF energy = -3596.48530565 hartree
ZPE = 0.676138 hartree
--------------------------------------------------------
Atom Coordinates (Angstroms)
X Y Z
--------------------------------------------------------
Fe 6.791402 2.424005 0.087002
Si -0.632051 2.638885 1.333870
C -0.292503 3.251569 3.092719
H 0.730155 3.620159 3.214950
H -0.979838 4.020535 3.454375
H -0.405619 2.383080 3.754284
C 0.788008 1.426582 0.996825
H 1.717936 1.971320 0.795936
H 0.947375 0.816733 1.895110
H 0.601373 0.745643 0.163580
C -2.272791 1.697066 1.418278
H -2.199252 0.858698 2.122117
H -3.072912 2.356951 1.773569
H -2.589013 1.290135 0.453131
Si -0.983658 3.550146 -1.589171
C 0.241175 4.419360 -2.738845
H 0.036133 5.481066 -2.888245
H 1.266368 4.323746 -2.363002
H 0.205883 3.937390 -3.723931
C -2.762296 3.956557 -2.094203
H -3.031356 5.002708 -1.920241
H -2.915610 3.750627 -3.160755
H -3.471039 3.337525 -1.531768
C -0.743193 1.709407 -1.977116
H -1.074653 1.562235 -3.012994
H 0.308961 1.412087 -1.932032
H -1.322329 1.022927 -1.354220
N -0.710193 3.944698 0.127354
C 4.290255 -1.170199 0.690684
C 4.436316 -1.198377 -0.839600
C 4.840844 0.237361 -1.158541
O 5.608537 0.681791 0.008216
C 5.440369 -0.262466 1.116560
H 3.328918 -0.729144 0.974495
H 4.361335 -2.160867 1.147016
H 3.515465 -1.486843 -1.352764
H 5.226798 -1.895182 -1.138804
H 5.479732 0.342038 -2.037116
H 3.974445 0.899267 -1.259729
H 5.246296 0.316550 2.020970
H 6.381289 -0.810528 1.233499
Si 8.043281 2.899582 2.209268
C 9.869907 2.334065 2.128133
H 10.396181 2.802561 1.288651
H 10.403960 2.603949 3.049597
H 9.951997 1.248073 2.001544
C 8.083401 4.776051 2.573628
H 8.556843 5.332613 1.756682
H 7.073809 5.182018 2.705487
67
H 8.650794 4.983906 3.491107
C 7.316803 2.078960 3.785268
H 6.281531 2.393119 3.964342
H 7.327320 0.984335 3.715432
H 7.903609 2.356247 4.671918
Si 6.865391 3.912521 -1.931435
C 6.361296 3.080966 -3.586218
H 5.321323 2.733073 -3.568517
H 6.454667 3.791428 -4.419230
H 6.998931 2.218892 -3.816475
C 5.727853 5.442600 -1.755402
H 4.673045 5.156550 -1.667972
H 5.983099 6.030808 -0.866522
H 5.823453 6.100877 -2.629892
C 8.628221 4.597104 -2.215370
H 8.980391 5.170858 -1.350498
H 9.350655 3.791823 -2.391590
H 8.650442 5.263953 -3.088163
Si -0.832261 5.640722 0.672882
C -2.443028 5.913305 1.631144
H -2.553829 5.252085 2.495910
H -2.499321 6.945719 1.997779
H -3.307939 5.746672 0.978263
C -0.865567 6.883946 -0.754609
H -1.626275 6.694679 -1.516088
H -1.091617 7.861655 -0.310164
H 0.105408 6.972919 -1.250214
C 0.652634 6.170365 1.717318
H 1.592194 5.859821 1.246291
H 0.666135 7.265425 1.782398
H 0.641461 5.783619 2.738127
--------------------------------------------------------
68
Supplementary Methods
1. Experimental Details
General Method. GLC analyses were carried out on a Shimadzu GC-2014 instrument
equipped with a flame-ionization detector using a CBP10 fused silica capillary column (25 m
x 0.25 mm). GC-MS spectra were recorded on a Shimadzu GC-2010/PARVUM2 instrument.
Solvents were dried over appropriate reagents and distilled prior to use. Sodium (30wt%
dispersion in toluene, Across Organics) and lithium (30wt% dispersion in paraffin, Kanto
Chemical) metals were washed with hexane and then with THF, and were stored in an argon-
filled glovebox. Chlorotrimethylsilane were distilled before use. Ferrocene was sublimated
before use. Complexes [Fe(CO)4(SiMe3)2],16 [Fe3(CO)12],46 [{η5-C5H4(SiMe3)}2Fe],47 and
[{η5-C5H2(SiMe3)3}2Fe ]17 were prepared as described in the literatures.
Catalytic Reduction of N2 into N(SiMe3)3 in the Presence of Fe(CO)5. A typical
procedure (Supplementary Table S1, run 1) is as follows. To a suspension of sodium (1.38
g, 60 mmol) in THF (40 mL) were added Me3SiCl (7.6 mL, 60 mmol) and Fe(CO)5 (13.2 µL,
0.10 mmol) under dinitrogen atmosphere. The mixture was stirred at room temperature (22-
24 °C) for 20 h under a gentle stream of dinitrogen. To the reaction mixture was added
cyclododecane (0.100 g) as an internal standard for GLC analysis. After stirring for 5 min,
the mixture was centrifuged to remove insoluble materials. The resultant clear supernatant
was subjected to GLC and GC-MS analyses. Then the supernatant was stirred with an
aqueous solution of H2SO4 (0.5 M, 10 mL) for 12 h. After the addition of an aqueous
solution of KOH (30 wt %, 10 mL), ammonia was distilled into an aqueous solution of
H2SO4 (0.5 M, 10 mL) under reduced pressure. The amount of ammonia was determined by
the indophenol method.48
69
Separately, we confirmed that the following Fe-complexes such as [(η5-C5H4R)2Fe] (R =
Me, tBu), FeCl2, and [Fe{N(SiMe3)2}2] did not work as effective catalysts under the same
reaction conditions (Supplementary Table S2).
Time Profile of Catalytic Formation of N(SiMe3)3 from N2. To a suspension of
sodium (1.38 g, 60 mmol) in THF (40 mL) were added Me3SiCl (7.6 mL, 60 mmol), Fe(CO)5
(13.2 µL, 0.10 mmol), and cyclododecane (0.102 g) under dinitrogen atmosphere. The
mixture was stirred at room temperature under a gentle stream of dinitrogen. An aliquot of
the reaction mixture was periodically analyzed by GLC (Supplementary Table S3).
2. Computational details
1. Fe(SiMe3)2X (X = thf (I), Cl– (I')), and their N2 complexes (II and II'). Optimized
structures of the proposed catalytic complexes I and I' as well as their N2 complexes (II and
II') are presented in Supplementary Figure S1. Both I and I' have a triangular structure and
their electronic ground state is triplet. The quintet and singlet states are higher in energy than
the triplet state by 4.1 and 33.0 kcal/mol for I, and 5.4 and 37.5 kcal/mol for I', respectively.
The Fe–N2 complexes II and II' adopt a slightly deformed tetrahedral structure. The N≡N
bond distance (rNN) and the N≡N stretching frequency (νNN) are calculated to be 1.126 Å and
2122 cm–1 for II, and 1.131 Å and 2082 cm–1 for II'. These values suggest that the
coordinated N2 molecule is activated in both the systems (cf. rNN = 1.098 Å and νNN = 2422
cm–1 for free N2 molecule). For the Fe–N2 complexes, the electronic ground state is quintet,
and the triplet state lies 4.3 (II) and 1.9 (II') kcal/mol above the quintet state. The N2-
binding energy in the Fe–thf system is 3.7 kcal/mol (quintet) and 12.1 kcal/mol (triplet),
while the N2 binding energy in the Fe–Cl system is only 0.3 kcal/mol (quintet) and 7.7
70
kcal/mol (triplet). Based on the strength of the Fe–N2 bond, the triplet state of
Fe(SiMe3)2(thf) (I) should be a better candidate for the catalyst of the N2 conversion.
2. Optimized structures of intermediates and energy profile for each reaction step in the
catalytic transformation of N2 into N(SiMe3)3 by I. Supplementary Figure S2 shows the
calculated catalytic cycle and energy profile of the transformation of N2 into N(SiMe3)3
catalyzed by I. Supplementary Figures S3-S10 describes energy profiles for each reaction
step presented in Supplementary Figure S2, together with optimized structures of reactant
complexes, transition states (TS), and product complexes. Selected interatomic distances of
the optimized structures are given in Å and hydrogen atoms are omitted for clarity in the
Supplementary Figures.
As shown in Supplementary Figure S2, the proposed reaction pathway for the conversion of
N2 into N(SiMe3)3 involves 10 iron complexes I-X, where a Me3Si radical is assumed to
work as an active species generated in situ from Na and Me3SiCl. The catalytic cycle starts
with the N2 binding to I. The difference in the SCF energy between I–N2 and TS is
estimated to be only 0.01 kcal/mol in the triplet state and it reverses by considering the zero-
point energy correction. Thus, we regard that the N2 addition has no activation barrier. A
sequential addition of two trimehylsilyl radicals to the distal N atom of the coordinated N2 in
II proceeds to form IV via III (Supplementary Figures S3 and S4). The addition of a silyl
radical to the distal N atom of IV results in the formation of V, in which the activation energy
is calculated to be relatively high (12.0 kcal/mol) due to steric hindrance among bulky silyl
ligands (Supplementary Figure S5). The N–N bond in V is readily cleaved to generate the
71
first molecule of N(SiMe3)3 and VI derived from a nitrido (Fe≡N) intermediate
(Supplementary Figure S6). The nitrido intermediate [Fe(SiMe3)2(thf)(N)] cannot be
optimized and the two silyl ligands on the Fe atom are spontaneously migrated to the N atom,
resulting in the formation of [Fe(N(SiMe3)2)(thf)] VI. The next silyl radical attacks the Fe
atom of VI to form VII. We could not optimize a reactant complex VI–SiMe3 even though
the geometry optimization started from the Fe–Si distance of 7 Å. This reaction virtually has
no activation barrier and thus the energy change were calculated using a thermochemical
equation VI + Me3Si = VII. After the addition of SiMe3 radical to VII (Supplementary
Figure S7), one of the silyl groups on the Fe atom migrates to the N atom to form IX having
the N(SiMe3)3 group as a ligand (Supplementary Figure S8). This migration process
temporally liberates the coordinated THF molecule. The formation of X from IX and SiMe3
is followed by the release of the second molecule of N(SiMe3)3 and the regeneration of I.
(Supplementary Figures S9 and S10). The highest activation energy in all the reaction steps
is 19.0 kcal/mol calculated for VIII → IX, which is reasonably low for a reaction that
proceeds at root temperature. In conclusion, the computational results suggest that the Fe(II)
complex I bearing two Me3Si groups is capable of serving as a suitable catalyst for the
transformation of N2 into N(SiMe3)3
72
Supplementary References
46. W. McFarlane, G. Wilkinson, Inorg. Synth. 8, 181 (1966).
47. A. F. Cunningham Jr. J. Am. Chem. Soc. 113, 4864 (1991).
48. A. L. Chaney, E. P. Marbach, Clinical Chem. 8, 130 (1962).