Suppor
ting
Information
Novel
Silicate
Platform
as Weakly-Coordinating
Anions
for Diverse
Organometallic
and Electrochemical
Applications
T. He, M. A. Bruening,
M. Espinosa,
T. Agapie*
1
Novel Silicate Platform as Weakly
-
Coordinating Anions
for
Diverse
Organometallic and Electrochemical Applications
Tianyi He,
†
Meaghan A. Bruening,
†
Matthew Espinosa,
Theodor Agapie*
†
Denotes equal contribution
Division of Chemistry and Chemical Engineering, California Institute of Technology, 1200 E. California
Boulevard, Pasadena, California, 91125, United States
Supporting Information
General Considerations
-
S
ynthesis
5
General Considerations
-
E
lectrochemical
Characterization
5
Experimental
Procedures
Synthesis of
[Et
3
NH][
Me
Si
F
24
]/1
-
[Et
3
NH]
,
[Me
2
NHPh][
Me
Si
F
24
]/1
-
[Me
2
NHPh]
,
[Et
3
NH][
Ph
Si
F
24
]/2
-
[Et
3
NH]
, and
[Me
2
NHPh][
Ph
Si
F
24
]/2
-
[Me
2
NHPh]
7
Synthesis of
(
3,5
-
t
Bu
2
C
6
H
3
)
SiCl
3
,
(
4
-
t
BuC
6
H
4
)SiCl
3
, and
(4
-
styrene)SiCl
3
9
Synthesis of
[Et
3
N
H][
t
Bu2
Ar
Si
F
24
]/3
-
[Et
3
NH]
,
[Et
3
NH][
CH2CH2(CF2)5CF3
Si
F
24
]/4
-
[Et
3
NH],
[Et
3
NH][
Decyl
Si
F
24
]/5
-
[Et
3
NH]
,
[Et
3
N
H][
Sty
Si
F
24
]/6
-
[Et
3
NH]
,
[Et
3
NH][
Vinyl
Si
F
24
]/7
-
[Et
3
NH]
,
[Et
3
NH][
tBu
Ar
Si
F
24
]/8
-
[Et
3
NH
]
,
[Et
3
NH][
Cy
Si
F
24
]/
9
-
[Et
3
NH]
,
and
[Et
3
NH][
CH2CF2CF3
Si
F
24
]/1
0
-
[Et
3
NH]
9
Synthesis of
[Mg(DME)
3
][
Me
Si
F
24
]
2
/
1
-
[Mg]
and
[Mg(DME)
3
][
Ph
Si
F
24
]
2
/2
-
[Mg]
12
Synthesis of
[K][
Me
Si
F
24
]/1
-
[K]
13
Synthesis of
[Na][
t
Bu2
Ar
Si
F
24
]/3
-
[Na] and [K][
t
Bu2
Ar
Si
F
24
]
/3
-
[K]
1
4
Synthesis of
[Bu
4
N][
Me
Si
F
24
]
/1
-
[Bu
4
N]
1
5
Synthesis of
[Ag][
M
e
Si
F
24
]/1
-
[Ag]
15
Synthesis of
[Ph
3
C][
t
Bu2
Ar
Si
F
24
]/3
-
[Ph
3
C]
16
Synthesis of
[Fc][
Me
Si
F
24
]/1
-
[Fc]
1
7
Synthesis of
[Ni(COD)
2
][
Me
Si
F
24
]/1
-
[Ni(COD)
2
]
17
Synthesis of
[Pd(dppe)(
NCMe)Me][
t
Bu2
Ar
Si
F
24
]/3
-
[Pd(dppe)(NCMe)Me]
17
Polymerization Trials
1
9
Procedure for Determining Solubility
1
9
Special
C
onsiderations for Mg
D
eposition/
S
tripping
E
lectrochemistry
20
Figure S
1
.
CV experiment of 0.26 M
1
-
[Mg(DME)
3
]
with 10 mM
of Me
2
Mg
in DME
2
1
Figure S
2
.
CV experiment of 0.26 M
1
-
[Mg(DME)
3
]
with 10 mM of Me
2
Mg
in DME
2
2
Figure S
3
.
CV experiment of 0.26 M
1
-
[Mg(DME)
3
]
with 10 mM of Me
2
Mg
in DME
2
3
Figure S
4
.
CV experiment of 0.26 M
1
-
[Mg(DME)
3
]
in DME
2
4
Figure S
5
.
Coulombic efficiencies for 0.26 M
1
-
[Mg(DME)
3
]
with 10 mM Me
2
Mg in DME
2
5
Figure S
6
.
Coulombic efficiencies for 0.26 M
1
-
[Mg(DME)
3
]
in
DME
2
5
Mg
D
eposition/
S
tripping experiments with
2
-
[Mg
(DME)
3
]
in DME
26
Figure S7
.
CV experiment of 0.25 M
2
-
[Mg(DME)
3
]
with 10 mM of Me
2
Mg in DME
26
Figure S8
. Cou
lombic efficiencies for
0.25 M
2
-
[Mg(DME)
3
]
with 10 mM of Me
2
Mg in DME
27
Determination of Trigonal Bipyramidal vs. Square Pyramidal Geometry
2
8
Figure S
9
.
1
H NMR spectrum of
[Et
3
NH][
Me
Si
F
24
]/1
-
[Et
3
NH]
in CD
3
CN
2
9
2
Figure S
10
.
19
F NMR spectrum of
[Et
3
NH][
Me
Si
F
24
]/1
-
[Et
3
NH]
in CD
3
CN
2
9
Figure S
11
.
13
C NMR spectrum of
[Et
3
NH][
Me
Si
F
24
]/1
-
[Et
3
NH]
in CD
3
CN
30
Figure S
1
2
.
29
Si NMR spectrum of
[Et
3
NH][
Me
Si
F
24
]/1
-
[Et
3
NH]
in CD
3
CN
30
Figure S
1
3
.
1
H NMR spectrum of
[Et
3
NH][
Ph
Si
F
24
]/2
-
[Et
3
NH]
in CD
3
CN
31
Figure S
1
4
.
19
F NMR spectrum of
[Et
3
NH][
Ph
Si
F
24
]/2
-
[Et
3
NH]
in CD
3
CN
31
Figure S
1
5
.
13
C NMR spectrum of
[Et
3
NH][
Ph
Si
F
24
]/2
-
[Et
3
NH]
in CD
3
CN
32
Figure S
1
6
.
29
Si NMR spectrum of
[Et
3
NH][
Ph
Si
F
24
]/2
-
[Et
3
NH]
in CD
3
CN
32
Figure S
1
7
.
1
H NMR spectrum of
[Me
2
NHPh][
Me
Si
F
24
]/1
-
[Me
2
NHPh]
in CD
3
CN
3
3
Figure S
1
8
.
19
F NMR spectrum of
[Me
2
NHPh][
Me
Si
F
24
]/1
-
[Me
2
NHPh]
in CD
3
CN
3
3
Figure S
1
9
.
13
C NMR
spectrum of
[Me
2
NHPh][
Me
Si
F
24
]/1
-
[Me
2
NHPh]
in CD
3
CN
3
4
Figure S
20
.
29
Si NMR spectrum of
[Me
2
NHPh][
Me
Si
F
24
]/1
-
[Me
2
NHPh]
in CD
3
CN
3
4
Figure S
21
.
1
H NMR spectrum of
[Me
2
NHPh][
Ph
Si
F
24
]/2
-
[Me
2
NHPh]
in CD
3
CN
3
5
Figure S
2
2
.
19
F NMR spectrum of
[Me
2
NHPh][
Ph
Si
F
24
]/2
-
[Me
2
NHPh]
in CD
3
CN
3
5
Figure S
2
3
.
13
C NMR spectrum of
[Me
2
NHPh][
Ph
Si
F
24
]/2
-
[Me
2
NHPh]
in CD
3
CN
3
6
Figure S
2
4
.
29
Si NMR spectrum of
[Me
2
NHPh][
Ph
Si
F
24
]/2
-
[Me
2
NHPh]
in CD
3
CN
3
6
Figure S
2
5
.
1
H NMR spectrum of
[Et
3
NH][
t
Bu2
Ar
Si
F
24
]/3
-
[Et
3
NH]
in CD
3
CN
3
7
Figure S
2
6
.
19
F NMR spectrum of
[Et
3
NH][
t
Bu2
Ar
Si
F
24
]/3
-
[Et
3
NH]
in CD
3
CN
3
7
Figure S
2
7
.
13
C NMR spectrum of
[Et
3
NH][
t
Bu2
Ar
Si
F
24
]/3
-
[Et
3
NH]
in CD
3
CN
3
8
Figure S
2
8
.
1
H
29
Si HMBC spectrum
of
[Et
3
NH][
t
Bu2
Ar
Si
F
24
]/3
-
[Et
3
NH]
in
CD
3
CN
3
8
Figure S
2
9
.
1
H NMR spectrum of
[Et
3
NH][
CH2CH2(CF2)5CF3
Si
F
24
]/4
-
[Et
3
NH]
in CD
3
CN
3
9
Figure S
30
.
19
F NMR spectrum of
[Et
3
NH][
CH2CH2(CF2)5CF3
Si
F
24
]/4
-
[Et
3
NH]
in CD
3
CN
3
9
Figure S
31
.
13
C NMR spectrum of
[Et
3
NH][
CH2CH2(CF2)5CF3
Si
F
24
]/4
-
[Et
3
NH]
in CD
3
CN
40
Figure S
3
2
.
29
Si NMR spectrum of
[Et
3
NH][
CH2CH2(CF2)5CF3
Si
F
24
]/4
-
[Et
3
NH]
in CD
3
CN
40
Figure S
3
3
.
1
H NMR spectrum of
[Et
3
NH][
Decyl
Si
F
24
]/5
-
[Et
3
NH]
in CD
3
CN
41
Figure S
3
4
.
19
F NMR spectrum of
[Et
3
NH][
Decyl
Si
F
24
]/5
-
[Et
3
NH]
in CD
3
CN
41
Figure S
3
5
.
13
C NMR spectrum of
[Et
3
NH][
Decyl
Si
F
24
]/5
-
[Et
3
NH]
in CD
3
CN
42
Figure S
3
6
.
29
Si NMR spectrum of
[Et
3
NH][
Decyl
Si
F
24
]/5
-
[Et
3
NH]
in CD
3
CN
42
Figure S
3
7
.
1
H NMR spectrum of
[Et
3
NH][
Styrene
Si
F
24
]/6
-
[Et
3
NH]
in CD
3
CN
4
3
Figure S
3
8
.
19
F NMR spectrum of
[Et
3
NH][
Styrene
Si
F
24
]/6
-
[Et
3
NH]
in CD
3
CN
4
3
Figure S
3
9
.
13
C NMR spectrum of
[Et
3
NH][
Styrene
Si
F
24
]/6
-
[Et
3
NH]
in CD
3
CN
4
4
Figure S
40
.
29
Si NMR spectrum of
[Et
3
NH][
Styrene
Si
F
24
]/6
-
[Et
3
NH]
in
CD
3
CN
4
4
Figure S
41
.
1
H NMR spectrum of
[Et
3
NH][
Vinyl
Si
F
24
]/7
-
[Et
3
NH]
in CD
3
CN
4
5
Figure S
4
2
.
19
F NMR spectrum of
[Et
3
NH][
Vinyl
Si
F
24
]/7
-
[Et
3
NH]
in CD
3
CN
4
5
Figure S
4
3
.
13
C NMR spectrum of
[Et
3
NH][
Vinyl
Si
F
24
]/7
-
[Et
3
NH]
in CD
3
CN
4
6
Figure S
4
4
.
29
Si NMR spectrum of
[Et
3
NH][
Vinyl
Si
F
24
]/7
-
[Et
3
NH]
in CD
3
CN
4
6
Figure S
4
5
.
1
H NMR spectrum of
[Et
3
NH][
tBu
Ar
Si
F
24
]/8
-
[Et
3
NH]
in CD
3
CN
4
7
Figure S
4
6
.
19
F NMR spectrum of
[Et
3
NH][
tBu
Ar
Si
F
24
]/8
-
[Et
3
NH]
in CD
3
CN
4
7
Figure S
4
7
.
13
C NMR spectrum of
[Et
3
NH][
tBu
Ar
Si
F
24
]/8
-
[Et
3
NH]
in CD
3
CN
4
8
Figure S
4
8
.
29
Si NMR spectrum of
[Et
3
NH][
tBu
Ar
Si
F
24
]/8
-
[Et
3
NH]
in CD
3
CN
4
8
Figure S
4
9
.
1
H NMR spectrum of
[Et
3
NH][
Cy
Si
F
24
]/9
-
[Et
3
NH]
in CD
3
CN
4
9
Figure S
50
.
19
F NMR spectrum of
[Et
3
NH][
Cy
Si
F
24
]/9
-
[Et
3
NH]
in CD
3
CN
4
9
Figure S
51
.
13
C NMR spectrum of
[Et
3
NH][
Cy
Si
F
24
]/9
-
[Et
3
NH]
in CD
3
CN
50
Figure S
5
2
.
29
Si NMR spectrum of
[Et
3
NH][
Cy
Si
F
24
]/9
-
[Et
3
NH]
in CD
3
CN
50
3
Figure S
5
3
.
1
H NMR spectrum of
[Et
3
NH][
C
H2CH2CF3
Si
F
24
]/10
-
[Et
3
NH]
in CD
3
CN
51
Figure S
5
4
.
19
F NMR spectrum of
[Et
3
NH][
C
H2CH2CF3
Si
F
24
]/10
-
[Et
3
NH]
in CD
3
CN
51
Figure S
5
5
.
13
C NMR spectrum of
[Et
3
NH][
C
H2CH2CF3
Si
F
24
]/10
-
[Et
3
NH]
in CD
3
CN
52
Figure S
5
6
.
29
Si NMR spectrum of
[Et
3
NH][
C
H2CH2CF3
Si
F
24
]/10
-
[Et
3
NH]
in CD
3
CN
52
Figure S
5
7
.
1
H NMR spectrum of
[Mg(DME)
3
][
Me
Si
F
24
]
2
/1
-
[Mg]
in CD
3
CN
5
3
Figure S
5
8
.
19
F NMR spectrum of
[Mg(DME)
3
][
Me
Si
F
24
]
2
/1
-
[Mg]
in CD
3
CN
5
3
Figure S
5
9
.
13
C NMR spectrum of
[Mg(DME)
3
][
Me
Si
F
24
]
2
/1
-
[Mg]
in CD
3
CN
5
4
Figure S
60
.
29
Si NMR
spectrum of
[Mg(DME)
3
][
Me
Si
F
24
]
2
/1
-
[Mg]
in CD
3
CN
5
4
Figure S
61
.
1
H NMR spectrum of
[Mg(DME)
3
][
Ph
Si
F
24
]
2
/
2
-
[Mg]
in CD
3
CN
55
Figure S6
2
.
1
H NMR spectrum of
[Mg(DME)
3
][
Ph
Si
F
24
]
2
/
2
-
[Mg]
in CD
3
CN
55
Figure S6
3
.
1
H NMR spectrum of
[Mg(DME)
3
][
Ph
Si
F
24
]
2
/
2
-
[Mg]
in CD
3
CN
56
Figure S6
4
.
1
H NMR spectrum of
[Mg(DME)
3
][
Ph
Si
F
24
]
2
/
2
-
[Mg]
in CD
3
CN
56
Figure S
6
5
.
1
H NMR spectrum of
[K][
Me
Si
F
24
]/1
-
[K]
in CD
3
CN
57
Figure S6
6
.
19
F NMR spectrum of
[K][
Me
Si
F
24
]/1
-
[K]
in CD
3
CN
5
7
Figure S6
7
.
13
C NMR
spectrum of
[K][
Me
Si
F
24
]/1
-
[K]
in CD
3
CN
5
8
Figure S6
8
.
29
Si NMR spectrum of
[K][
Me
Si
F
24
]/1
-
[K]
in CD
3
CN
5
8
Figure S6
9
.
1
H NMR spectrum of
[Na][
t
Bu2
Ar
Si
F
24
]/3
-
[Na]
in CD
3
CN
59
Figure S
70
.
19
F NMR spectrum of
[Na][
t
Bu2
Ar
Si
F
24
]/3
-
[Na]
in CD
3
CN
59
Figure S
71
.
13
C NMR spectrum of
[Na][
t
Bu2
Ar
Si
F
24
]/3
-
[Na]
in CD
3
CN
60
Figure S
7
2
.
1
H
29
Si HMBC spectrum of
[Na][
t
Bu2
Ar
Si
F
24
]/3
-
[Na]
in CD
3
CN
60
Figure S
7
3
.
1
H NMR spectrum of
[K][
t
Bu2
Ar
Si
F
24
]/3
-
[K]
in CD
3
CN
61
Figure S
7
4
.
19
F
NMR spectrum of
[K][
t
Bu2
Ar
Si
F
24
]/3
-
[K]
in CD
3
CN
61
Figure S
7
5
.
13
C NMR spectrum of
[K][
t
Bu2
Ar
Si
F
24
]/3
-
[K]
in CD
3
CN
62
Figure S
7
6
.
1
H
29
Si HMBC spectrum of
[K][
t
Bu2
Ar
Si
F
24
]/3
-
[K]
in CD
3
CN
62
Figure S7
7
.
1
H NMR spectrum of
[Bu
4
N][
Me
Si
F
24
]/1
-
[Bu
4
N]
in CD
3
CN
63
Figure S7
8
.
19
F NMR spectrum of
[Bu
4
N][
Me
Si
F
24
]/1
-
[Bu
4
N]
in CD
3
CN
63
Figure S7
9
.
13
C NMR spectrum of
[Bu
4
N][
Me
Si
F
24
]/1
-
[Bu
4
N]
in CD
3
CN
64
Figure S
80
.
29
Si NMR spectrum of
[Bu
4
N][
Me
Si
F
24
]/1
-
[Bu
4
N]
in CD
3
CN
64
Figure S
81
.
1
H NMR spectrum of
[Ag(MeCN)
2
][
Me
Si
F
24
]/1
-
[Ag]
in CD
2
Cl
2
6
5
Figure S
8
2
.
19
F NMR spectrum of
[Ag(MeCN)
2
][
Me
Si
F
24
]/1
-
[Ag]
in CD
2
Cl
2
6
5
Figure S
8
3
.
13
C NMR spectrum of
[Ag(MeCN)
2
][
Me
Si
F
24
]/1
-
[Ag]
in CD
2
Cl
2
6
6
Figure S
8
4
.
29
Si
NMR spectrum of
[Ag(MeCN)
2
][
Me
Si
F
24
]/1
-
[Ag]
in CD
2
Cl
2
6
6
Figure S
8
5
.
1
H NMR spectrum of
[Ph
3
C][
t
Bu2
Ar
Si
F
24
]/3
-
[Ph
3
C]
in CD
2
Cl
2
6
7
Figure S8
6
.
19
F NMR spectrum of
[Ph
3
C][
t
Bu2
Ar
Si
F
24
]/3
-
[Ph
3
C]
in CD
2
Cl
2
6
7
Figure S
8
7
.
13
C NMR spectrum of
[Ph
3
C][
t
Bu2
Ar
Si
F
24
]/3
-
[Ph
3
C]
in CD
2
Cl
2
6
8
Figure S
8
8
.
29
Si NMR spectrum of
[Ph
3
C][
t
Bu2
Ar
Si
F
24
]/3
-
[Ph
3
C]
in CD
2
Cl
2
6
8
Figure S
8
9
.
1
H NMR spectrum of
[Fc][
Me
Si
F
24
]/1
-
[Fc]
in CD
3
CN
6
9
Figure S
90
.
19
F NMR spectrum of
[Fc][
Me
Si
F
24
]/1
-
[Fc]
in CD
3
CN
6
9
Figure S
91
.
X
-
band CW EPR spectrum of
1
-
[Ni(COD)
2
]
70
Crystallography refinement details
71
Table S1.
Crystal and refinement data
72
Figure S
9
2
.
X
-
ray crystal structure of
1
-
[Et
3
NH]
7
5
Figure S
9
3
.
X
-
ray
crystal structure of
3
-
[Et
3
NH]
7
5
4
Figure S
9
4
.
X
-
ray crystal structure of
1
-
[
Fc
]
7
6
Figure S
9
5
.
X
-
ray crystal structure of
3
-
[
Ph
3
C
]
7
6
Figure S
9
6
.
X
-
ray crystal structure of
1
-
[Ag(NCMe)
2
]
7
7
Figure S
9
7
.
X
-
ray crystal structure of
3
-
[
K]
7
7
Figure S
9
8
.
X
-
ray crystal structure of
1
-
[
Mg
(
DME
)
3
]
7
8
Figure S
9
9
.
X
-
ray crystal structure of
1
-
[
Ni(COD)
2
]
7
9
Figure S
100
.
X
-
ray crystal structure of
7
-
[
Et
3
NH]
7
9
References
80