of 35
S1
Supporting Information
Exploring the Limits of Dative Boratrane Bonding: Iron as a
Strong Lewis Base in Low-Va
lent Non-Heme Iron-Nitrosyl
Complexes
Hai T. Dong
1
; Matthew J. Chalkley
2
; Paul H. Oyala
2
; Jiyong Zhao
3
; E. Ercan Alp
3
; Michael Y. Hu
3
; Jonas C.
Peters
2,
*; Nicolai Lehnert
1,
*
1
Department of Chemistry and Department of Biophysics, University of Michigan, Ann Arbor, Michigan 48109-
1055, United States
2
Department of Chemistry and Chemical Engineering, California Institute of Technology, Pasadena, California
91125, United States
3
Advanced Photon Source (APS), Argonne National Laborato
ry (ANL), Argonne, Illinois 60439, United States
E-mail:
lehnertn@umich.edu, jpeters@caltech.edu
S2
Table of Contents
Figure S1 Exp. NRVS data vs. ca
lculated spectra using BP86/TZVP ..................................... S3
Figure S2 Crystal stru
cture top vs. side view ........................................................................... S
4
Pulse EPR data and simulations:
Pulse EPR data interpretation and simulation details ............................................................... S5
Figure S3 HYSCORE powder pattern ...................................................................................... S6
Figure S4 EPR simulations with EasySpin ............................................................................... S7
CW-EPR data ...............................................................................................................
............. S8
Figure S5 X-band HYSCORE spectra of ls-{FeNO}
9
complex at 290 mT ............................. S9
Figure S6 X-band HYSCORE spectra of ls-{FeNO}
9
complex at 327 mT .......................... S10
Figure S7 X-band HYSCORE spectra of ls-{FeNO}
9
complex at 347 mT .......................... S11
Figure S8 Field-Depende
nt Davies ENDOR spectra and
31
P simulations of [Fe(TPB)(NO)] S12
DFT-optimized structures (coordinates):
Table S1 Exp. data vs. B3LYP DFT results ............................................................................ S13
DFT coordinates ...........................................................................................................
.... S14-S31
Figure S9-11 Quasi-rest
ricted orbitals of ls-{FeNO}
8-10
................................................ S32-S34
References
S3
Figure S1.
Experimental NRVS VDOS data of the ls-{FeNO}
8
complex [Fe(TPB)(NO)](BAr
F
4
)
(purple), the ls-{FeNO}
9
complex [Fe(TPB)(NO)] (brown) and the ls-{FeNO}
10
complex [Na(12-
crown-4)
2
][Fe(TPB)(NO)] (red) vs BP
86/TZVP DFT calculated spectra (black). The BP86
calculations reproduce th
e vibrational properties of the ls-{FeNO}
8-10
complexes, especially the
Fe-NO and N-O stretching frequencies, quite
well compared to experiment. The observed
deviations of 10-30 cm
-1
for the Fe-NO stretches are very
reasonable for DFT frequency
calculations.
1
Importantly, the calculati
ons capture the unusual lack of correlation between the
change in Fe-NO and N-O stretchi
ng frequencies along the ls-{FeNO}
8-10
series (Fe-NO stretch:
610/583/602 cm
-1
(exp.) vs. 638/621/633cm
-1
(BP86); N-O stretch: 1745/1667/1568 cm
-1
(exp.)
vs. 1751/1692/1607 cm
-1
(BP86)). Thus, we use these calcula
tions as the basis to further analyze
the NRVS data and refine the force constants of
the Fe-N-O units in the three complexes.
S4
Figure S2.
Top down view and side view of the
crystral structures of the ls-{FeNO}
8-10
series.
2
S5
Pulse EPR data interpretation and simulation details:
In general, the ENDOR spectrum for a given nucleus with spin
= ½ (
1
H,
31
P) coupled to the S =
½ electron spin exhibits
a doublet at frequencies
2
(1)
Where
is the nuclear Larmor frequency and
is the hyperfine couplin
g constant. For nuclei
with
1
(
2
H), an additonal splitting of the
manifolds is produced
by the nuclear quadrupole
interaction (P)
,
3
푃ሺ
2
1
2
(2)
In HYSCORE spectra, these signals manifest as
cross-peaks or ridges in the 2-D frequency
spectrum which are generally symmetric about the
diagonal of a given quadrant. This technique
allows hyperfine levels corresponding to th
e same electron-nuclear submanifold to be
differentiated, as well as separa
ting features from hype
rfine couplings in th
e weak-coupling regime
(
|
|
2
|
|
) in the (+,+) quadrant from thos
e in the strong coupling regime (
|
|
2
|
|
) in the
(
,+) quadrant. The (
,
) and (+,
) quadrants of these frequency spectra are symmetric to the (+,+)
and (
,+) quadrants, thus typically only two of the qua
drants are displayed in the literature. For
systems with appreciable hyperfine anisotropy in
frozen solutions or solids, HYSCORE spectra
typically do not exhibit sharp cross peaks, but sh
ow ridges that represent the sum of cross peaks
from selected orientations within the excitation
bandwidth of the MW pulses at the magnetic field
position at which the spectrum is collected. The length and curvature of these correlation ridges
can allow for the separation and estimation of
the magnitude of the isotropic and dipolar
components of the hyperfine tens
or, as shown in Figure S3.
S6
Figure S3.
a) HYSCORE powder patterns for an
S
= 1/2,
I
= 1/2 spin system with an isotropic
hyperfine tensor A. b) HYSCO
RE powder patterns for an
S
= 1/2,
I
= 1/2 spin system with an
isotropic hyperfine tensor
which contains isotropic (
௜௦௢
) and dipolar (
) contributions. Blue
correlation ridges represent the
strong coupling case; red correla
tion ridges represent the weak
coupling case.
S7
EPR Simulations
. Simulations of all CW and pulse EPR
data were achieved using the EasySpin
3
simulation toolbox (release 5.2.21) with Matl
ab 2018b using the following Hamiltonian:
ൌ휇
푔푆
൅휇
൅ℎ푆
∙퐼
൅ℎ퐼
∙푷∙퐼
(3)
In this expression, the first term corresponds to
the electron Zeeman interaction term where
is
the Bohr magneton, g is the electron spin g-va
lue matrix with principle components g = [g
xx
, g
yy
,
g
zz
], and
is the electron spin oper
ator; the second term corres
ponds to the nuclear Zeeman
interaction term where
is the nuclear magneton,
is the characteristic nuclear g-value for
each nucleus (e.g.
1
H,
2
H,
31
P) and
is the nuclear spin operator; the third term corresponds to the
electron-nuclear hyperfine term, where
is the hyperfine coupling
tensor with principle
components
= [A
xx
, A
yy
, A
zz
]; and for nuclei with
1
, the final term corresponds to the
nuclear quadrupole (NQI) term wh
ich arises from the interac
tion of the nuclear quadrupole
moment with the local electric field
gradient (efg) at the nucleus, where
is
the
quadrupole
coupling tensor. In the principle axis system (PAS),
is traceless and parametrized by the
quadrupole coupling constant
푄푞
/
and the asymmetry parameter
such that:
푷ൌ
௫௫
00
0
௬௬
0
00
௭௭
푄푞
/
4
퐼ሺ
2
퐼െ
1
െሺ
1
െ휂ሻ
00
0
െሺ
1
൅휂ሻ
0
002
(4)
where
ொ௤
2
2
퐼െ
1
௭௭
and
휂ൌ
ೣೣ
ି௉
೤೤
೥೥
. The asymmetry parameter may have values
between 0 and 1, with 0 corresponding to an elec
tric field gradient with axial symmetry and 1
corresponding to a fully rhombic efg.
The orientations between the hyperfine and NQI te
nsor principle axis sy
stems and the g-matrix
reference frame are defined by the Euler angles (
α
,
β
,
γ
).
S8
CW EPR data:
Figure S4.
Pseudomodulated X-band ESE-EPR spectrum of the ls-{FeNO}
9
complex
[Fe(TPB)(
15
NO)] (black) with simulation overlaid (red).
Arrows denote field positions at which
pulse EPR data were acquired.
Acquisition parameters: Temperat
ure = 7 K; microwave frequency = 9.711 GHz; MW pulse length
(
π
/2,
π
) = 160 ns, 80 ns;
τ
= 300 ns; shot repeti
tion time (srt) = 1 ms.
S9
Figure S5.
X-band HYSCORE spectra of the ls-{FeNO}
9
complex [Fe(TPB)(
14/15
NO)]. The
experimental data are plotted in co
lor in the top panels,
ranging from dark blue
to red in increasing
intensity. These same data are plotted in grey in the bottom panels, with
14/15
N and
11
B simulations
overlaid in red and green, respec
tively. Unsimulated features cente
red around 15 MHz in the (+,+)
quadrant arise from weakly coupled
1
H nuclei of the ligand or from solvent.
Acquisition parameters: Temperature = 7
K; microwave frequency = 9.711 GHz; B
0
= 290 mT (
g
= 2.393); MW pulse length (
π
/2,
π
) = 8 ns, 16 ns;
τ
= 142 ns; t
1
= t
2
= 100 ns;
Δ
t
1
=
Δ
t
2
= 16 ns;
shot repetition time (srt) = 1 ms.
S10
Figure S6.
X-band HYSCORE spectra of the ls-{FeNO}
9
complex [Fe(TPB)(
14/15
NO)]. The
experimental data are plotted in co
lor in the top panels,
ranging from dark blue
to red in increasing
intensity. These same data are plotted in grey in the bottom panels, with
14/15
N and
11
B simulations
overlaid in red and green, respec
tively. Unsimulated features cente
red around 15 MHz in the (+,+)
quadrant arise from weakly coupled
1
H nuclei of the ligand or from solvent.
Acquisition parameters: Temperature = 7
K; microwave frequency = 9.711 GHz; B
0
= 327 mT (
g
= 2.122); MW pulse length (
π
/2,
π
) = 8 ns, 16 ns;
τ
= 142 ns; t
1
= t
2
= 100 ns;
Δ
t
1
=
Δ
t
2
= 16 ns;
shot repetition time (srt) = 1 ms.
S11
Figure S7.
X-band HYSCORE spectra of the ls-{FeNO}
9
complex [Fe(TPB)(
14/15
NO)]. The
experimental data are plotted in co
lor in the top panels,
ranging from dark blue
to red in increasing
intensity. These same data are plotted in grey in the bottom panels, with
14/15
N and
11
B simulations
overlaid in red and green, respec
tively. Unsimulated features cente
red around 15 MHz in the (+,+)
quadrant arise from weakly coupled
1
H nuclei of the ligand or from solvent.
Acquisition parameters: Temperature = 7
K; microwave frequency = 9.711 GHz; B
0
= 347 mT (
g
= 2.000); MW pulse length (
π
/2,
π
) = 8 ns, 16 ns;
τ
= 136 ns; t
1
= t
2
= 100 ns;
Δ
t
1
=
Δ
t
2
= 16 ns;
shot repetition time (srt) = 1 ms.
S12
Figure S8.
Field-Dependent Davies ENDOR spectra and
31
P simulations of [Fe(TPB)(NO)].
Acquisition parameters: Temp
erature = 5 K; microwave frequency = 9.730 GHz; B
0
= 308 mT (
g
= 2.257), 327 mT (
g
= 2.126), 347 mT (
g
= 2.003); MW pulse length (
π
/2,
π
) = 40 ns, 80 ns; RF
pulse length = 40 μs; RF delay t
RF
= 2 μs;
τ
= 340 ns; shot repetition time (srt) = 20 ms.
S13
Table S1.
Experimental structural and
NRVS data of the ls-{FeNO}
8
complex vs. B3LYP/TZVP
closed shell (CS) and broken symmetry (BS) results.
ls-{FeNO}
8
Exp.
B3LYP (CS) B3LYP (BS)
d(N
O)
1.16 1.17 1.17
d(Fe

O)
1.66 1.65 1.68
d(Fe
B)
2.31 2.37 2.37
Fe
N
O
176 172 175
d(Fe
P)
2.28 2.35 2.37
d(Fe
P)
2.28 2.35 2.37
d(Fe
P)
2.29 2.36 2.36
P-Fe-P
100 100 100
P-Fe-P
101 101 101
P-Fe-P
154 152 152
(Fe
NO)
610 654 490
(N-O)
1745 1810 1793
(Fe-N-O)
537 529 442
(Fe-N-O)
540 537 461
S14
Table S2.
Optimized coordinates of the ls-{FeNO}
8
complex in the closed-shell state with
BP86/TZVP
Fe -0.05211700 -0.58037100 0.57287600
N -0.08444900 -1.48549100 1.96141600
O -0.12932800 -2.02647000 3.00833400
H -4.65434100 0.58675100 0.79021700
H -5.44858500 -0.83677100 0.07135800
H -5.52866100 0.73188400 -0.74148500
H -3.06015700 -1.07727400 -2.93316100
H -4.66401300 -0.31573400 -2.86425400
H -4.41693400 -1.91572100 -2.13893100
H -3.13767800 0.73954900 -1.22705600
H -4.39533500 -1.43744200 2.27762000
P -0.33472600 1.66933200 1.03634600
P 2.26683600 -0.70342400 0.34099600
P -2.24081300 -1.11786100 -0.00778400
B 0.12683800 0.53761000 -1.44888900
C -0.97462200 1.68433700 -1.57559800
C -1.27723600 2.38752400 -0.39125700
C -2.14191900 3.49211500 -0.39632600
C -2.73421000 3.89666600 -1.59871700
C -2.44666600 3.21158100 -2.78604000
C -1.56576300 2.12262400 -2.77699400
C 1.62951100 1.01846000 -1.73807000
C 2.72546200 0.42767200 -1.05780900
C 4.04732400 0.76696200 -1.39419600
C 4.30263800 1.71074400 -2.39472600
C 3.23535400 2.32533100 -3.05564300
C 1.92056700 1.98259400 -2.72455400
C -0.09234400 -1.00238200 -1.78868200
C -1.06348600 -1.87951800 -1.18583600
C -1.07150900 -3.26725600 -1.49533900
C -0.24462100 -3.77782200 -2.48189600
C 0.65929500 -2.92581300 -3.14923000
C 0.77474300 -1.60216000 -2.75967500
C -2.84780400 1.81475400 2.44487800
C -1.34907400 2.09036500 2.60073400
C -0.83832300 1.39238000 3.87107400
C 1.76851100 3.00628200 2.58037000
C 1.17383800 2.86756600 1.17068600
C 0.88392400 4.26358500 0.59839400
C 2.76619700 -0.53388900 3.17335900
C 3.36757100 -0.16412700 1.80887700
C 4.84002000 -0.61345400 1.75934900
C 2.70155100 -3.45471800 1.06303400
C 2.73343100 -2.48963400 -0.13312400
S15
C 4.02461700 -2.63206500 -0.95285000
C -4.06559500 -3.38291700 0.28207200
C -2.99115700 -2.54202400 0.99714200
C -3.50502100 -2.07495700 2.37096300
C -3.94737700 -0.93568700 -2.30196700
C -3.61345300 -0.21914300 -0.98365600
C -4.87293000 0.07122200 -0.15310600
H -2.35693700 4.04847800 0.51850400
H -3.41668200 4.74899600 -1.60867600
H -2.91053900 3.53044400 -3.72233300
H -1.35212000 1.59834200 -3.71264800
H 4.89277000 0.30695500 -0.88446200
H 5.33327300 1.96892700 -2.64636300
H 3.42767800 3.07279900 -3.82867000
H 1.09555700 2.47198500 -3.24824100
H -1.76445300 -3.93753000 -0.98807500
H -0.30714200 -4.83426300 -2.75176400
H 1.27880500 -3.31429300 -3.96049400
H 1.51242000 -0.96577300 -3.25080200
H -3.29313500 2.31434400 1.57646800
H -3.37843300 2.16324400 3.34529700
H -3.03333800 0.73439200 2.35791900
H -1.19847200 3.18038700 2.70598700
H -1.39780700 1.77208000 4.74065900
H 0.22561700 1.56031700 4.06966000
H -1.01073600 0.30849800 3.82218800
H 2.01729200 2.04725400 3.05088900
H 1.09403700 3.55432500 3.25488500
H 2.69922500 3.59211600 2.51482300
H 1.91679200 2.38660800 0.51610600
H 0.58607000 4.23513700 -0.45614700
H 1.79920400 4.87212100 0.67538900
H 0.09843300 4.78817300 1.16503900
H 1.74394300 -0.15836600 3.30004500
H 3.38684200 -0.09419000 3.97026200
H 2.75024000 -1.62039000 3.33650400
H 3.34581300 0.93283100 1.70455800
H 5.35980000 -0.33394400 0.83616300
H 4.94384800 -1.69784200 1.89845800
H 5.37676900 -0.12824300 2.59023700
H 1.76175100 -3.39970100 1.62795300
H 3.53384300 -3.28681500 1.76045700
H 2.79820200 -4.48598900 0.68855700
H 1.89481000 -2.75562500 -0.79397500
H 4.02842400 -1.98332400 -1.83894000
H 4.10589400 -3.67382700 -1.30301100
S16
H 4.92480300 -2.41627300 -0.36139000
H -3.77704600 -3.70849700 -0.72554100
H -5.01740100 -2.84188100 0.19886600
H -4.26051200 -4.28669600 0.88124700
H -2.10400300 -3.17553200 1.16746200
H -2.74460900 -1.52912200 2.94398900
H -3.79458400 -2.95598800 2.96455100
S17
Table S3.
Optimized coordinates of the ls-{FeNO}
9
complex in the closed-shell state with
BP86/TZVP
Fe 0.05214600 -0.03547700 -1.07312100
N -0.03304400 -0.02020200 -2.73541600
O -0.18593200 -0.02126000 -3.91846000
H 2.57725100 0.23026000 -3.19284600
H 2.85263000 -1.49898700 -3.47763800
H 4.20686000 -0.35698200 -3.60211200
H 5.02543800 -2.03587000 -0.35724100
H 5.67286900 -1.42718000 -1.89251100
H 4.51816500 -2.76723700 -1.89072800
H 4.00625900 0.17743500 -1.16273600
H 2.82936100 -3.87213400 -1.95152500
P 0.21143900 2.18831300 -0.51278600
P -2.11281100 -0.85066600 -0.57414600
P 2.06454800 -1.02738400 -0.47410100
B -0.04218200 -0.05308800 1.34837500
C -0.93231900 1.24310900 1.76020400
C -0.87459300 2.41556000 0.97015300
C -1.58025200 3.57671600 1.31958300
C -2.37900300 3.59017400 2.47067300
C -2.45172800 2.44467000 3.27065900
C -1.73559600 1.29281900 2.91891500
C -0.78094800 -1.44404700 1.72434900
C -1.87976300 -1.88450800 0.94494900
C -2.63916300 -3.00459500 1.31911500
C -2.29258800 -3.74000300 2.45888900
C -1.19423900 -3.34212600 3.22819800
C -0.45855600 -2.20726600 2.86698500
C 1.46308700 0.03793400 1.95100100
C 2.56637400 -0.44106900 1.20807900
C 3.87359800 -0.38703700 1.71868200
C 4.10971800 0.14972000 2.98952400
C 3.03329900 0.61936800 3.74955300
C 1.73295800 0.55945000 3.23462300
C 1.73197000 4.35665900 0.69920800
C 1.85500600 2.93740900 0.12985600
C 3.01758800 2.84417600 -0.87067700
C 0.47346400 3.53175800 -3.03692000
C -0.39572800 3.48402900 -1.77004000
C -1.86005200 3.24951400 -2.15490500
C -4.32017100 0.74422900 -1.52052100
C -3.59323600 0.32031900 -0.23325200
C -4.57581900 -0.17591200 0.83735100
C -1.66787500 -3.00906000 -2.36409500
C -2.73979200 -1.98488700 -1.97730300
S18
C -4.09870000 -2.68967900 -1.80998700
C 2.65962200 -3.61176000 0.77704200
C 1.78386100 -2.91601600 -0.27400100
C 1.80360800 -3.66862700 -1.61429600
C 4.76558500 -1.81596600 -1.40032500
C 3.63235900 -0.78409700 -1.55204100
C 3.28930200 -0.59035900 -3.03661700
H -1.52735800 4.47271900 0.69539300
H -2.94316900 4.48770400 2.73555300
H -3.07636300 2.44617800 4.16822200
H -1.81413600 0.40310800 3.55138200
H -3.49936500 -3.32034100 0.72913700
H -2.87442000 -4.62196600 2.73723000
H -0.91285200 -3.91587200 4.11557200
H 0.38936000 -1.90094800 3.48636400
H 4.72304700 -0.73886300 1.13123900
H 5.12957800 0.20708000 3.37751600
H 3.20935400 1.04530400 4.74111000
H 0.90641700 0.95522900 3.83176300
H 0.96095300 4.42538600 1.47850400
H 1.50268300 5.09613400 -0.08530500
H 2.69209300 4.65447800 1.15298000
H 2.06735100 2.25094100 0.96407500
H 3.04145200 3.71198200 -1.54640100
H 2.95769400 1.93917100 -1.49009900
H 3.97860200 2.82672800 -0.33185500
H 1.50867000 3.82954600 -2.83258100
H 0.05078800 4.26392800 -3.74495000
H 0.49203200 2.55632200 -3.54435100
H -0.31619200 4.45438400 -1.24960800
H -1.95978700 2.31451300 -2.72526400
H -2.52283100 3.19323500 -1.28091400
H -2.21524700 4.07106500 -2.79891200
H -3.62694100 1.03747200 -2.32033000
H -4.96024300 1.61550500 -1.30651500
H -4.97223500 -0.04929200 -1.91257800
H -3.08288900 1.20618900 0.17415200
H -5.11870200 -1.08081500 0.52506500
H -4.06870300 -0.39581300 1.78601500
H -5.32531500 0.60952900 1.03134500
H -0.71573400 -2.52070900 -2.60432900
H -1.99110100 -3.58009200 -3.24988000
H -1.49165100 -3.72606000 -1.54713400
H -2.82975100 -1.25997200 -2.80516300
H -4.00907600 -3.58637000 -1.18073000
H -4.88059000 -2.04995000 -1.38352100
S19
H -4.45197400 -3.02966700 -2.79793100
H 2.62739400 -3.09517800 1.74547600
H 3.71056100 -3.68215600 0.46041100
H 2.29159400 -4.63988700 0.93207300
H 0.74892400 -2.92035900 0.10541600
H 1.28598900 -3.12383500 -2.41547600
H 1.30181700 -4.64317800 -1.50013200
S20
Table S4.
Optimized coordinates of the ls-{FeNO}
10
complex in the closed-shell state with
BP86/TZVP
Fe -0.00059000 0.00012300 -1.08463800
N -0.00048800 -0.00167200 -2.73690100
O -0.00005200 -0.00342200 -3.94914100
P 1.23211900 -1.81007700 -0.61305800
P 0.95078700 1.97244600 -0.61384400
P -2.18438700 -0.16067300 -0.61300100
B -0.00035900 -0.00036800 1.37269600
C 1.36291400 -0.74551700 1.88840200
C 2.04863300 -1.65318000 1.04576600
C 3.22484400 -2.30003400 1.46017400
C 3.75645100 -2.05485800 2.73290400
C 3.09184700 -1.17150700 3.59071100
C 1.91684400 -0.53470700 3.17083800
C -0.03508400 1.55255900 1.88842400
C 0.40871600 2.60025000 1.04601400
C 0.38266800 3.94202000 1.46150100
C -0.09401300 4.27944000 2.73487000
C -0.52740900 3.26215800 3.59231100
C -0.49322300 1.92646300 3.17149000
C -1.32733200 -0.80861400 1.88778800
C -2.45604600 -0.94888700 1.04486200
C -3.60405800 -1.64471600 1.45900800
C -3.65716700 -2.22847100 2.73142600
C -2.56012000 -2.09420100 3.58949300
C -1.42165400 -1.39385600 3.17018000
C 1.63412200 -4.75998100 -0.49086300
C 0.57363500 -3.64587200 -0.51670300
C -0.36669800 -3.83971200 0.67666300
C 2.16508500 -2.65940500 -3.18384400
C 2.68258400 -2.15103500 -1.82794300
C 3.57038800 -0.92163300 -2.03075700
C 3.30545600 3.79474700 -0.49336000
C 2.87045800 2.31933500 -0.51829000
C 3.50815000 1.60229300 0.67544500
C 1.21755200 3.20383100 -3.18436100
C 0.52025100 3.39863400 -1.82769400
C -0.98859300 3.55454700 -2.02911800
C -4.93913700 0.96702500 -0.48699600
C -3.44401700 1.32826900 -0.51102500
C -3.14107500 2.23331300 0.68686600
C -3.38567600 -0.53915800 -3.18450700
C -3.20535100 -1.24326700 -1.82937300
C -2.58598200 -2.62738900 -2.03393600
H 3.75552500 -2.97386400 0.78176900
S21
H 4.68692400 -2.53841700 3.04431100
H 3.50145100 -0.96264000 4.58426300
H 1.43810700 0.18167700 3.84570200
H 0.70126900 4.73870100 0.78353300
H -0.13902200 5.32688400 3.04699100
H -0.91201000 3.51228400 4.58632900
H -0.87496500 1.15355600 3.84582100
H -4.45308000 -1.76709000 0.78071600
H -4.54087400 -2.79318300 3.04247400
H -2.58395900 -2.55373000 4.58288000
H -0.56214700 -1.33679900 3.84535800
H 2.28555400 -4.77283900 -1.37567000
H 1.12855200 -5.74170900 -0.44258000
H 2.26851100 -4.68238600 0.40603900
H -0.01605200 -3.74465200 -1.44330100
H -1.16923000 -3.09478700 0.70476400
H 0.18444100 -3.76162400 1.62660900
H -0.82623600 -4.84344400 0.63635300
H 1.55699100 -3.57156300 -3.09406200
H 3.01715800 -2.89329300 -3.84704200
H 1.55375000 -1.89576300 -3.68484400
H 3.29544400 -2.94174500 -1.36277300
H 4.01243900 -0.57444800 -1.08650700
H 2.98555100 -0.09479600 -2.45982700
H 4.39489300 -1.15878800 -2.72708400
H 2.99029300 4.36519900 -1.37812200
H 4.40849700 3.84753700 -0.44588200
H 2.92183300 4.30579200 0.40360900
H 3.25044600 1.85766800 -1.44496500
H 3.26170300 0.53545400 0.70568200
H 3.16704800 2.04284500 1.62508100
H 4.60738200 1.70349300 0.63381100
H 2.31176800 3.13532400 -3.09584900
H 0.99171200 4.05722600 -3.84863700
H 0.86293100 2.29107100 -3.68339400
H 0.89994000 4.32450800 -1.36318600
H -1.51021300 3.75912300 -1.08369900
H -1.41342200 2.63759300 -2.46354400
H -1.19491400 4.39112500 -2.72086200
H -5.27584300 0.41340100 -1.37447600
H -5.53654400 1.89549400 -0.43427000
H -5.18905600 0.37451200 0.40711100
H -3.23430700 1.89236800 -1.43513900
H -2.09414000 2.55406200 0.71732200
H -3.35012600 1.71224400 1.63403400
H -3.77932500 3.13420000 0.65083400
S22
H -3.87162400 0.44342300 -3.09386700
H -4.01372600 -1.15921900 -3.84906700
H -2.41818500 -0.39107400 -3.68437700
H -4.19686000 -1.37815800 -1.36484500
H -2.50361700 -3.18386900 -1.08994700
H -1.57885900 -2.53541900 -2.46652800
H -3.20638700 -3.22245700 -2.72814400
S23
Table S5.
Optimized coordinates of the ls-{FeNO}
8
complex in the broken-symmetry state with
B3LYP/TZVP
Fe -0.04384400 -0.54803900 0.65283800
N -0.06973100 -1.43476700 2.07697700
O -0.09400400 -1.95637300 3.12180600
P -0.27017900 1.78857800 0.96886700
P 2.29358400 -0.74513900 0.36711500
P -2.27488100 -1.09306800 0.07541600
B 0.12562700 0.43941600 -1.49002800
C -0.94289400 1.61173200 -1.63323500
C -1.20219000 2.40302500 -0.50453800
C -2.03862100 3.51714600 -0.58043000
C -2.64453000 3.84493100 -1.78930600
C -2.40160800 3.06876800 -2.91941200
C -1.55237800 1.96828800 -2.84328200
C 1.63871400 0.86476800 -1.79592300
C 2.72885400 0.32160100 -1.08321800
C 4.04067600 0.65428600 -1.43252400
C 4.29516700 1.52926200 -2.48287000
C 3.23347600 2.08523600 -3.18532000
C 1.92756300 1.75909000 -2.83689700
C -0.18576700 -1.09699800 -1.77719400
C -1.19998100 -1.90177100 -1.17558600
C -1.30627500 -3.26885500 -1.49634700
C -0.51341600 -3.83471400 -2.47365600
C 0.44489400 -3.05361200 -3.12630500
C 0.63308500 -1.74196000 -2.74552600
C -2.75049700 2.13040900 2.43571300
C -1.23486000 2.32180700 2.52247700
C -0.72535600 1.64781700 3.80441400
C 0.98357900 4.33886200 0.42722400
C 1.26162400 2.94844600 1.01073900
C 1.92137600 3.09676700 2.38628700
C 2.86125000 -0.48300900 3.16442700
C 3.45116800 -0.20076300 1.77676600
C 4.89853300 -0.71616600 1.72886000
C 3.94638600 -2.75974500 -0.92694100
C 2.68174200 -2.54827500 -0.08682800
C 2.64103500 -3.49248800 1.12242100
C -3.44864700 -1.92654500 2.52143500
C -3.01846800 -2.46491000 1.14689900
C -4.15608400 -3.30000000 0.53852800
C -4.12001900 -0.96480100 -2.12006200
C -3.66832000 -0.20262800 -0.86805000
C -4.86312800 0.18661300 0.01123100
H -2.22102800 4.13876700 0.28682800
S24
H -3.30091900 4.70398300 -1.84913500
H -2.87450300 3.32324200 -3.86032700
H -1.37594700 1.37461200 -3.73352800
H 4.88030300 0.24343600 -0.89291700
H 5.31665600 1.77874000 -2.74110400
H 3.42116600 2.77476600 -3.99939900
H 1.11220800 2.20972200 -3.38910900
H -2.03626500 -3.88865300 -0.99875800
H -0.64320500 -4.87683400 -2.73871700
H 1.04923600 -3.48157800 -3.91668400
H 1.40774000 -1.16494000 -3.23117800
H -3.19131300 2.55259800 1.53644100
H -3.21869500 2.61649100 3.29532300
H -3.01306700 1.07423900 2.48717500
H -1.02917100 3.39504500 2.58865800
H 0.34029700 1.77359900 3.97161800
H -0.94311800 0.57967800 3.80139000
H -1.24239500 2.08213200 4.66378900
H 0.66403600 4.29974800 -0.61126800
H 1.90273200 4.92829000 0.47187600
H 0.22647700 4.88096600 0.99824900
H 1.96320100 2.44743300 0.34385600
H 2.14599500 2.14673000 2.86532700
H 1.30685500 3.68490400 3.06945600
H 2.86527800 3.63366500 2.26571500
H 1.86894300 -0.05803800 3.29290200
H 3.51216000 -0.04465500 3.92454500
H 2.79668400 -1.55111800 3.37131400
H 3.47957900 0.88111200 1.63138700
H 5.40783800 -0.52372200 0.78847400
H 4.95767500 -1.78432000 1.93327500
H 5.46849300 -0.20880200 2.51109600
H 3.95565500 -2.13996200 -1.82271300
H 3.98284300 -3.80379800 -1.24829200
H 4.85852700 -2.56273100 -0.36447400
H 1.82978000 -2.79789700 -0.71955300
H 1.72081900 -3.40121800 1.69743900
H 3.48213000 -3.33948700 1.79769800
H 2.69996200 -4.52319800 0.76498000
H -2.66142400 -1.36484400 3.02022900
H -3.71062000 -2.76659200 3.16853100
H -4.32973800 -1.28927700 2.44518900
H -2.15453400 -3.11712700 1.30134200
H -3.94221900 -3.68362900 -0.45690100
H -5.08508100 -2.73495100 0.48129800
H -4.34298400 -4.15864900 1.18810200
S25
H -3.29367800 -1.17094900 -2.79917600
H -4.84507500 -0.34978800 -2.65908400
H -4.60913800 -1.90856700 -1.87851300
H -3.18485000 0.71468900 -1.19394100
H -4.57173400 0.72951700 0.90756800
H -5.45877200 -0.67511500 0.30981600
H -5.51618200 0.84337500 -0.56783400
S26
Table S6.
Optimized coordinates of the ls-{FeNO}
8
complex in the closed-shell state with
B3LYP/TZVP
Fe -0.04990000 -0.55430600 0.63555400
N -0.07894000 -1.38717800 2.05547500
O -0.12410800 -1.83369500 3.13073700
P -0.28719500 1.75694200 0.97033200
P 2.28524500 -0.74143400 0.37023100
P -2.26428200 -1.10633300 0.06505800
B 0.13152100 0.46343900 -1.49212900
C -0.94289400 1.62841300 -1.63481300
C -1.21627000 2.39729200 -0.49445000
C -2.06112600 3.50575600 -0.55695400
C -2.66110600 3.84874100 -1.76459000
C -2.40372500 3.09435300 -2.90628000
C -1.54536100 2.00008900 -2.84345000
C 1.64541200 0.89076500 -1.78430000
C 2.73001900 0.33047800 -1.07533900
C 4.04453500 0.65502400 -1.42143100
C 4.30708700 1.53985100 -2.46176600
C 3.25106500 2.11527900 -3.15682600
C 1.94213800 1.79606200 -2.81317800
C -0.16330800 -1.07597100 -1.77228100
C -1.17042000 -1.89593900 -1.17813700
C -1.25542800 -3.26493700 -1.50210500
C -0.45463800 -3.81616600 -2.48024500
C 0.49490700 -3.02007900 -3.12882900
C 0.66820400 -1.70980300 -2.73968000
C -2.77471700 2.07711300 2.43119700
C -1.26089000 2.28141700 2.52148900
C -0.75257500 1.62094200 3.81081400
C 0.97037700 4.30698900 0.43325900
C 1.24332200 2.92125900 1.03036200
C 1.88551900 3.08304700 2.41272400
C 2.84760700 -0.47827200 3.17093000
C 3.43838700 -0.19484100 1.78401900
C 4.88679600 -0.70796800 1.74009600
C 3.95099000 -2.76158200 -0.90370500
C 2.67861900 -2.54440300 -0.07691600
C 2.62168300 -3.48351900 1.13560200
C -3.46385600 -1.96990900 2.49056900
C -3.00876700 -2.49175900 1.11771700
C -4.13001900 -3.33155800 0.48554700
C -4.08524700 -0.96877500 -2.14889400
C -3.65306200 -0.21579200 -0.88430800
C -4.86167900 0.15564700 -0.01592900
H -2.25522100 4.11102900 0.31922900
S27
H -3.32459400 4.70306000 -1.81459100
H -2.87243500 3.36098300 -3.84588600
H -1.35720400 1.42347000 -3.74246400
H 4.88066100 0.22999900 -0.88759500
H 5.33102500 1.78206100 -2.71758400
H 3.44542900 2.81360100 -3.96179300
H 1.13063700 2.25910600 -3.36085300
H -1.97737900 -3.89596400 -1.00724300
H -0.57126100 -4.85860600 -2.75013500
H 1.10402800 -3.43627700 -3.92175700
H 1.43667200 -1.12204400 -3.22169300
H -3.21649500 2.49077800 1.52852600
H -3.24936400 2.56431700 3.28666100
H -3.02934800 1.01915000 2.48831500
H -1.06587000 3.35698800 2.58169900
H 0.31302300 1.74616800 3.97806700
H -0.97308000 0.55397600 3.82154800
H -1.26866400 2.06671100 4.66462900
H 0.66747400 4.26042100 -0.60983200
H 1.88702700 4.89922400 0.48891000
H 0.20218900 4.85034100 0.98837700
H 1.95548100 2.41852300 0.37657400
H 2.11575800 2.13851500 2.89903900
H 1.25769500 3.66829500 3.08604800
H 2.82492800 3.62934600 2.29905700
H 1.85680600 -0.05092300 3.30093500
H 3.49962900 -0.04268500 3.93180300
H 2.78048400 -1.54655500 3.37650600
H 3.46579100 0.88723100 1.63971200
H 5.39894000 -0.51418000 0.80162700
H 4.94711400 -1.77608600 1.94451500
H 5.45340000 -0.19981200 2.52424700
H 3.97031700 -2.14433800 -1.80112800
H 3.98752400 -3.80658000 -1.22225500
H 4.85833300 -2.56582700 -0.33336200
H 1.83276600 -2.79519000 -0.71702500
H 1.69457800 -3.38548800 1.69886700
H 3.45531000 -3.33070400 1.82018100
H 2.68066400 -4.51602500 0.78357700
H -2.68713900 -1.41282500 3.01047000
H -3.73485600 -2.81841200 3.12263700
H -4.34537700 -1.33425800 2.40678000
H -2.14046600 -3.13673100 1.27888900
H -3.90010400 -3.70088100 -0.51181000
H -5.06390000 -2.77482000 0.42376600
H -4.31670900 -4.19969800 1.12244300
S28
H -3.24980600 -1.16320100 -2.82012900
H -4.80835200 -0.35322600 -2.68998500
H -4.57094000 -1.91782700 -1.92186400
H -3.17274000 0.70810900 -1.19538300
H -4.58624200 0.69243400 0.88913400
H -5.45405000 -0.71358200 0.26699200
H -5.51282600 0.81237800 -0.59721200
S29
Table S7.
Optimized coordinates of the {FeN
2
}
9
complex with BP86/TZVP
Fe 0.02872200 -0.02305000 -1.01287800
N 0.05219500 0.10160900 -2.80244100
N 0.07700400 0.16321300 -3.95070900
P -2.11031400 -0.83385900 -0.68283300
P 2.00460500 -1.07964500 -0.70610700
P 0.16068500 2.18324900 -0.50526500
B 0.01800400 -0.18612900 1.30232400
C -0.92738500 -1.46243300 1.71168300
C -2.00673100 -1.84831200 0.87348900
C -2.84511800 -2.92939900 1.19593300
C -2.63254400 -3.66879500 2.36608200
C -1.57866700 -3.30857200 3.21466100
C -0.75062400 -2.22834200 2.88861600
C 1.54600900 -0.37444000 1.88380000
C 2.59207300 -0.81284400 1.03282500
C 3.91063400 -0.96899800 1.49318900
C 4.23248700 -0.68310800 2.82552500
C 3.22091100 -0.25224000 3.69195800
C 1.90887800 -0.10681300 3.22413900
C -0.64256000 1.18923200 1.91211800
C -0.63977400 2.39176600 1.16010000
C -1.21333100 3.57431900 1.65750400
C -1.81112000 3.59524700 2.92423500
C -1.81906200 2.42554800 3.69310800
C -1.24481900 1.25150200 3.19002100
C -5.06860900 -0.81905900 -0.53820600
C -3.81779400 0.07345500 -0.48656600
C -3.86363300 0.91215600 0.79473900
C -3.06187300 -1.41615400 -3.31489400
C -2.63472200 -2.11470300 -2.01348200
C -1.51973800 -3.12989500 -2.28623100
C 3.44062000 -3.66020400 -0.78882500
C 2.04564600 -3.01621900 -0.84586700
C 1.15638100 -3.66597000 0.21766300
C 3.32110700 -1.20926400 -3.24006200
C 3.53311100 -0.70481700 -1.80280700
C 3.86174700 0.78928200 -1.81536300
C 1.57010800 4.78592000 -0.13424000
C 1.76821100 3.26414500 -0.24304500
C 2.56231500 2.79423300 0.98063900
C -0.01615700 3.61660000 -2.96994400
C -0.77103300 3.42284700 -1.64372400
C -2.21288800 2.98688100 -1.91303600
H -3.65045700 -3.22670800 0.51813300
H -3.27160100 -4.52448400 2.60252300
S30
H -1.39369300 -3.88294600 4.12849300
H 0.08338000 -1.98541000 3.55445400
H 4.70386100 -1.28245300 0.80807200
H 5.26333600 -0.78151800 3.17801200
H 3.45961100 -0.01324000 4.73352300
H 1.14570900 0.26625400 3.91413700
H -1.22777700 4.48153100 1.04709700
H -2.27701100 4.51119900 3.29940900
H -2.29121700 2.42470900 4.68109500
H -1.30048900 0.33934900 3.79316900
H -5.16866400 -1.38814300 -1.47272400
H -5.96819400 -0.18479000 -0.44197400
H -5.08315200 -1.52722000 0.30450800
H -3.83578400 0.75352400 -1.35388700
H -3.02644600 1.61440100 0.87578800
H -3.83342200 0.26568800 1.68498600
H -4.80466400 1.48922200 0.82895400
H -3.88417300 -0.70080000 -3.16365200
H -3.40717800 -2.16712000 -4.04773800
H -2.21999600 -0.87420500 -3.76808000
H -3.49939900 -2.66381700 -1.60308500
H -1.28131500 -3.71924000 -1.39004300
H -0.60066100 -2.62309000 -2.61763200
H -1.82970900 -3.83016300 -3.08222400
H 4.11391100 -3.32955100 -1.59188300
H 3.33992100 -4.75705300 -0.87482200
H 3.92790800 -3.45548000 0.17756500
H 1.60320400 -3.20945800 -1.83857000
H 0.14025100 -3.25683900 0.22122100
H 1.57142300 -3.50900300 1.22502600
H 1.09363000 -4.75479000 0.04402600
H 3.11801600 -2.28879900 -3.28848200
H 4.22600100 -1.01498200 -3.84301100
H 2.47985200 -0.69037900 -3.72129600
H 4.38507100 -1.24509400 -1.35522400
H 4.06153000 1.17587400 -0.80625000
H 3.01964100 1.35592700 -2.24005400
H 4.75295400 0.98061600 -2.43915300
H 1.10523400 5.23908000 -1.02060200
H 2.55428600 5.27055600 0.00180600
H 0.96268100 5.04457400 0.74721500
H 2.36271300 3.05588200 -1.14777200
H 2.76177600 1.71725900 0.97283400
H 2.01316700 3.01549800 1.90893700
H 3.53026900 3.32442600 1.02821200
H 1.01618100 3.96819700 -2.82503000