S
1
Tetranuclear Iron Clusters with A Varied Interstitial Ligand: Effects On Structure,
Redox Properties, and
N
itric Oxide
Activation
Christopher J. Reed, and Theodor Agapie*
Division of Chemistry and Chemical Engineering,
California Institute of Technology,
Pasadena, California 91125, United States, Email: agapie@caltech.edu
Supporting Information
S
2
Table of
Contents
Figure S1
.
1
H NMR spectrum (300 MHz) of KPhPz in CD
3
CN
................................
.................
S
4
Figure S2
.
13
C NMR spectrum (300 MHz) of KPhPz in CD
3
CN
................................
................
S
4
Figure S3
.
1
H NMR spectrum (300 MHz) of [LFe
3
F(PhPz)
3
Fe][OTf]
(
1
)
in CD
2
Cl
2
.................
S
5
Figure S4
.
19
F
NMR spectrum (300 MHz) of [LFe
3
F(
PhPz)
3
Fe][OTf]
(
1
)
in CD
2
Cl
2
................
S
5
Figure S5
.
1
H NMR spectrum (300 MHz) of [LFe
3
F(PhPz)
3
Fe][OTf]
2
(
2
)
in CD
2
Cl
2
...............
S
6
Figure S
6
.
1
9
F NMR spectrum (300 MHz) of [LFe
3
F(PhPz)
3
Fe][OTf]
2
(
2
)
in CD
2
Cl
2
...............
S
6
Figure S
7
.
1
H NMR spectrum (300 MHz) of [LFe
3
F(PhPz)
3
Fe
(
CH
3
CN
)
][OTf]
3
(
3
)
in CD
3
C
N
................................
................................
................................
................................
.......................
S
7
Figure S8
.
1
9
F NMR spectrum (300 MHz) of [LFe
3
F(PhPz)
3
Fe
(
CH
3
CN
)
][OTf]
3
(
3
)
in CD
3
C
N
................................
................................
................................
................................
.......................
S
7
Figure S9
.
1
H NMR spectrum (300 MHz) of [LFe
3
F(PhPz)
3
Fe
(NO)
][OTf]
(
1
-
NO
)
in
CD
2
Cl
2
................................
................................
................................
................................
...........
S
8
Figure S10
.
19
F NMR spectrum (300 MHz) of [LFe
3
F(PhPz)
3
Fe(NO)][OTf]
(
1
-
NO
)
in
CD
2
Cl
2
................................
................................
................................
................................
...........
S
8
Figure S11
.
1
H NMR spectrum (300 MHz) of [LFe
3
F(PhPz)
3
Fe(NO)][OTf]
2
(
2
-
NO
)
in
CD
2
Cl
2
................................
................................
................................
................................
...........
S
9
Figure S12
.
1
9
F NMR spectrum (300 MHz) of [LFe
3
F(PhPz)
3
Fe(NO)][OTf]
2
(
2
-
NO
)
in
CD
2
Cl
2
................................
................................
................................
................................
...........
S
9
Figure S13
.
1
H NMR spectrum (300 MHz) of [LFe
3
F(PhPz)
3
Fe(NO)][OTf]
3
(
3
-
NO
)
in
CD
2
Cl
2
................................
................................
................................
................................
.........
S
1
0
Figure S14
.
1
9
F NMR spectrum (300 MHz) of [LFe
3
F(PhPz)
3
Fe(NO)][OTf]
3
(
3
-
NO
)
in
CD
2
Cl
2
................................
................................
................................
................................
.........
S
1
0
Figure S15
.
1
H NMR spectrum (300 MHz) of [LFe
3
F(PhPz)
3
Fe(NO)][OTf]
3
[SbCl
6
]
(
4
-
NO
)
in
CD
3
CN
................................
................................
................................
................................
........
S
11
Figure S16
.
1
9
F NMR spectrum
(300 MHz) of [LFe
3
F(PhPz)
3
Fe(NO)][OTf]
3
[SbCl
6
]
(
4
-
NO
)
in
CD
3
CN
................................
................................
................................
................................
........
S
11
Figure S
17
.
1
H NMR spectrum (300 MHz) of reaction mixture of 6 equiv NO
addition
to
[LFe
3
F(PhPz)
3
Fe(NO)][OTf]
(
1
-
NO
)
................................
................................
.........................
S12
Figure S
18
.
1
H NMR spectrum (300 MHz) of reaction mixture of 6
equiv NO
addition
to
[LFe
3
F(PhPz)
3
Fe(NO)][OTf]
2
(
2
-
NO
)
................................
................................
........................
S12
Figure S
19
.
1
H NMR spectrum (300 MHz) of reaction mixture of 6 equiv NO
addition
to
[LFe
3
F(PhPz)
3
Fe(NO)][OTf]
3
(
3
-
NO
)
................................
................................
........................
S13
Figure S2
0
.
1
H NMR spectrum (300 MHz) of reaction mixture of AgOTf
addition
to
LFe
3
F(PhPz)
3
Fe(NO
)
(
5
-
NO
)
................................
................................
................................
.....
S13
Figure S2
1
.
1
H NMR spectrum (300 MHz) of reaction mixture of LFe
3
F(PhPz)
3
Fe(NO)
(
5
-
NO
)
decomposition
................................
................................
................................
.............................
S14
Figure S
2
2
. Solid state IR spectra of complexes
1,
1
-
NO
–
5
-
NO
................................
............
S
15
Figure S
2
3
. Electrochemistry of [LFe
3
F(PhPz)
3
Fe][
OTf]
(
1
)
in CH
3
CN
................................
..
S15
Figure S
2
4
.
Electrochemistry of [LFe
3
F(PhPz)
3
Fe(NO)][OTf]
(
1
-
NO
)
in CH
2
Cl
2
.................
S2
16
Figure S25
.
Current density (
j
p
) dependence of the square root of the scan rate
(
ν
1/2
)
for the CV
of
[LFe
3
F(PhPz)
3
Fe(NO)][OTf] (
1
-
NO
)
................................
................................
.....................
S16
M
ö
ssbauer
simulation details for compounds 1
–
3 and 1
-
NO
–
5
-
NO
................................
S17
Simulation details for [LFe
3
(PhPz)
3
FFe][OTf] (1) (Figure S2
6
)
................................
...........
S
17
Figure S
2
7
.
Zero applied field
57
Fe M
ö
ssbauer spectrum of [LFe
3
F(PhPz)
3
Fe][OTf]
(
1
)
.
S17
-
S18
S
3
Simulation details for [LFe
3
(PhPz)
3
FFe][OTf]
2
(2) (Figure S
2
8
)
................................
.........
S18
Figure
S
2
9
Zero applied field
57
Fe M
ö
ssbauer spectrum of [LFe
3
F(PhPz)
3
Fe][OTf]
2
.......
S18
-
S19
Simulation details for [LFe
3
(PhPz)
3
FFe(CH
3
CN)][OTf]
3
(3) (Figure S
30
)
..................
S19
-
S20
Figure S3
1
.
Zero applied field
57
Fe M
ö
ssbauer spectrum of
[LFe
3
F(PhPz)
3
Fe(CH
3
CN)][OTf]
3
................................
................................
..............................
S
20
Simulation details for LFe
3
(PhPz)
3
FFe(NO) (5
-
NO) (Figure S3
2
)
................................
.......
S
21
Figure S3
3
.
Zero applied field
57
Fe M
ö
ssbauer spectrum of LFe
3
F(PhPz)
3
Fe(NO)
.................
S
2
1
Simulation details for [LFe
3
(PhPz)
3
FFe(NO)][OTf] (1
-
NO) (Figure S3
4
)
...........................
S22
Figure S3
5
.
Zero applied field
57
Fe M
ö
ssbauer spectrum of [LFe
3
F(PhPz)
3
Fe(NO)][OTf]
.....
S
22
Simulation details for [LFe
3
(PhPz)
3
FFe(NO)][OTf]
2
(2
-
NO)
(Figure S3
6
)
.........................
S23
Figure S
3
7
.
Zero applied field
57
Fe M
ö
ssbauer spectrum of [LFe
3
F(PhPz)
3
Fe(NO)][OTf]
2
....
S
24
Simulation details for [LFe
3
(PhPz)
3
FFe(NO)][OTf]
3
(3
-
NO) (Figure S
3
8
)
..................
S24
-
S25
Figure S
3
9
.
Zero applied field
57
Fe M
ö
ssbauer spectrum of [LFe
3
F(PhPz)
3
Fe(NO)][OTf]
3
....
S
26
Simulation details for [LFe
3
(PhPz)
3
FFe(NO)][OTf]
3
[SbCl
6
] (4
-
NO)
................................
...
S26
Figure S
40
.
Zero
applied field
57
Fe M
ö
ssbauer spectrum of
[LFe
3
F(PhPz)
3
Fe(NO)][OTf]
3
[SbCl
6
]
................................
................................
.........................
S27
Figure S
4
1
. UV
-
Vis spectr
a
of [LFe
3
F(PhPz)
3
Fe][OTf]
(
1
)
in CH
2
Cl
2
................................
.....
S
27
Figure S
4
2
. UV
-
Vis spectr
a
of [LFe
3
F(PhPz)
3
Fe][OTf]
2
(
2
)
in CH
2
Cl
2
................................
...
S
28
Figure S
4
3
. UV
-
Vis spectr
a
of [LFe
3
F(PhPz)
3
Fe(
CH
3
CN)][OTf]
3
(
3
)
in CH
2
Cl
2
....................
S
28
Figure S
4
4
. UV
-
Vis spectr
a
of [LFe
3
F(PhPz)
3
Fe(NO)][OTf]
(
1
-
NO
)
in CH
2
Cl
2
.....................
S
29
Figure S
4
5
. UV
-
Vis spectr
a
of [LFe
3
F(PhPz)
3
Fe(NO)][OTf]
2
(
2
-
NO
)
in CH
2
Cl
2
....................
S
29
Figure S4
6
. UV
-
Vis spectra of [LFe
3
F(PhPz)
3
Fe(NO)][OTf]
3
(
3
-
NO
)
in CH
2
Cl
2
....................
S
30
Figure S
4
7
. UV
-
Vis spectra of [LFe
3
F(PhPz)
3
Fe(NO)][OTf]
3
[SbCl
6
]
(
4
-
NO
)
in CH
3
C
N
.......
S
3
0
Figure S
4
8
. Crystal structure of [LFe
3
F(PhPz)
3
Fe][OTf]
(
1
)
................................
....................
S
31
Special refinement details for [LFe
3
F(PhPz)
3
Fe][OTf]
................................
..............................
S
31
Figure S
4
9
. Crystal structure of
[LFe
3
F(PhPz)
3
Fe][OTf]
2
(
2
)
................................
...................
S
32
Special refinement details for [LFe
3
F(PhPz)
3
Fe][OTf]
2
................................
.............................
S
32
Figure S
50
. Crystal structure of [LFe
3
F(PhPz)
3
Fe(CH
3
CN)][OTf]
3
(
3
)
................................
....
S
33
Special refinement details for [LFe
3
F(PhPz)
3
Fe(CH
3
CN)][OTf]
3
................................
..............
S
33
Figure S
5
1
. Crystal structure
of [LFe
3
F(PhPz)
3
Fe(NO)][OTf]
(
1
-
NO
)
................................
....
S
34
Special refinement details for [LFe
3
F(PhPz)
3
Fe(NO)][OTf]
................................
......................
S
34
Figure S
5
2
. Crystal structure of [LFe
3
F(PhPz)
3
Fe(NO)][OTf]
2
(
2
-
NO
)
................................
...
S
35
Special refinement details for [LFe
3
F(PhPz)
3
Fe(NO)][OTf]
2
................................
....................
S
35
Figure S
5
3
. Crystal
structure of [LFe
3
F(PhPz)
3
Fe(NO)][OTf]
3
(
3
-
NO
)
................................
...
S
36
Special refinement details for [LFe
3
F(PhPz)
3
Fe(NO)][OTf]
3
................................
....................
S
36
Table S1
. Selected bond angles and distances for complexes
................................
....................
S
37
Table S2
. Crystal and refinement data for complexes
1
–
3
and
1
-
NO
–
3
-
NO
........................
S
38
Table S3
.
Reported
C
–
O Stretching Frequencies and Redox Potentials
for Iron Carbonyl
Clusters Bearing Various Interstitial Ligands
................................
................................
......
S39
-
S4
0
References
................................
................................
................................
...........................
S
41
-
S42
S
4
Figure S1
.
1
H NMR spectrum (300 MHz) of potassium 3
-
phenyl
pyrazolate in CD
3
CN
Figure S2
.
13
C NMR spectrum (300 MHz) of
potassium 3
-
phenyl pyrazolate
in CD
3
CN
S
5
Figure S3
.
1
H NMR spectrum (300 MHz) of [LFe
3
F(PhPz)
3
Fe][OTf]
(
1
)
in CD
2
Cl
2
Figure S4
.
19
F NMR spectrum (300 MHz) of [LFe
3
F(PhPz)
3
Fe][OTf]
(
1
)
in
CD
2
Cl
2
S
6
Figure S5
.
1
H NMR spectrum (300 MHz) of [LFe
3
F(PhPz)
3
Fe][OTf]
2
(
2
)
in CD
2
Cl
2
Figure S6
.
1
9
F NMR spectrum (300 MHz) of [LFe
3
F(PhPz)
3
Fe][OTf]
2
(
2
)
in CD
2
Cl
2
S
7
Figure S7
.
1
H NMR spectrum (300 MHz) of [LFe
3
F(PhPz)
3
Fe(
CH
3
CN
)][OTf]
3
(
3
)
in CD
3
C
N
Figure S8
.
1
9
F NMR spectrum (300 MHz) of [LFe
3
F(PhPz)
3
Fe(
CH
3
CN
)][OTf]
3
(
3
)
in CD
3
C
N
S
8
Figure S9
.
1
H NMR spectrum (300 MHz) of [LFe
3
F(PhPz)
3
Fe(NO)][OTf]
(
1
-
NO
)
in CD
2
Cl
2
Figure S10
.
19
F NMR spectrum (300 MHz) of [LFe
3
F(PhPz)
3
Fe(NO)][OTf]
(
1
-
NO
)
in CD
2
Cl
2
S
9
Figure S11
.
1
H NMR spectrum (300 MHz) of [LFe
3
F(PhPz)
3
Fe(NO)][OTf]
2
(
2
-
NO
)
in CD
2
Cl
2
Figure S12
.
1
9
F NMR spectrum (300 MHz) of [LFe
3
F(PhPz)
3
Fe(NO)][OTf]
2
(
2
-
NO
)
in CD
2
Cl
2