of 58
S
1
Supporting Information for
Switchable Synthesis of Ethylene/Acrylate Copolymers by A
Dinickel Catalyst: Evidence for Chain Growth on Both Nickel
Centers and Concepts of Cation
Exchange
Polymerization
Shuoyan Xiong
a
,
Heather A. Spinney
b
, Brad C. Bailey
b
, Briana S. Henderson
b
,
Adjeoda A. Tekpor
a
,
Matthew R. Espinosa
a
,
Paramita Saha
a
,
Theodor Agapie*
a
*To whom correspondence should be addressed, E
-
mail:
agapie@caltech.edu
a
Division of Chemistry and Chemical Engineering, California Institute of Technology, Pasadena, California 91125,
USA.
b
Chemical Science, Core R&D, The Dow Chemical Company, Midland, Michigan 48667, USA.
1.
General
c
onsiderations
S2
2
.
Synthesis of
l
igand
BINOL
-
(POH)
2
an
d complex
X
-
Ni
2
S
3
3
.
Cation binding studies
S
5
4
. NMR spectra
S
8
5. Cryst
al
lographic
i
nformation
S
1
4
6
.
Investigations of tBA insertion into
X
-
Ni
2
S
1
6
7
.
Kinetic studies of tBA insertion into
X
-
Ni
2
S
20
8
.
Investigations of tBA insertion into
in
-
situ
generated
Ni
2
Na
species
S
2
6
9. Procedures for polymerization and polymer characterization
S
2
9
10
.
Supplemental data for polymerization catalysis
S
3
2
11
.
Supplemental data for polymer
characterization
S
4
3
References
S
58
S
2
1
General Considerations
All air
-
and water
-
sensitive compounds were manipulated under N
2
or Ar using standard Schlenk or glovebox
techniques. The solvents for air
-
and moisture
-
sensitive reactions were dried over sodium benzophenone/ketyl,
calcium hydride, or by the method of Grubbs.
1
Deu
terated solvents were purchased from Cambridge Isotopes
Lab, Inc.; C
6
D
6,
was dried over a purple suspension with Na/benzophenone ketyl and vacuum transferred. t
-
Butyl acrylate was dried over 4 Å sieves for greater
than 72h. (±)
-
1,1'
-
Bi
-
2
-
naphthol,
2.5 M
n
B
uLi in hexanes
were purchased from Sigma
-
Aldrich and used without further purification.
C
hloromethyl methyl ether
solution
,
2
2,2
-
Bis(methoxymethoxy)
-
1,1
-
binaphthalene
,
3
b
is(dimethoxyphenyl)phosphine chloride,
4
and
py
2
Ni(CH
2
SiMe
3
)
2
5
were synthesized according to literature procedures. All
1
H,
13
C, and
31
P spectra of organic
and organometallic compounds were recorded on Varian INOVA
-
400, or Bruker Cryoprobe 400 spectrometers.
1
H and
13
C chemical shifts are reported relative to residu
al solvent resonances.
S
3
2 Synthesis of Ligand
BINOL
-
(POH)
2
and
X
-
Ni
2
Ligand
BINOL
-
(POH)
2
:
A Schlenk flask fitted with a screw
-
in Teflon stopper was charged with a solution of
2,2
-
bis(methoxymethoxy
)
-
1,1
-
binaphthalene (3.76 g, 10.0 mmol) in THF (40 mL) and cooled to
-
78 °C under
nitrogen. A hexane solution of
n
-
butyllithium (8.4 mL, 2.5 M, 21.0 mmol) was added dropwise via syringe. After
stirring for an additional 30 min at
-
78
°C
, the reaction was a
llow to warm up to 0 °C and stirred for an additional
4 h before cooled back to
-
78 °C. Next, a solution of bis(2,6
-
dimethoxyphenyl)phosphine chloride (6.82 g, 20.0
mmol) in THF (20 mL) was added dropwise via cannula. After complete addition, the reaction
was allowed to
warm up to room temperature and stirred for an additional 6 h, yielding a bright yellow solution. To this solution
was added degassed MeOH (10 mL) and concentrated aqueous HCl (10 mL, degassed by three freeze
-
pump
-
thaw
cycles with a liquid n
itrogen bath prior to usage). After stirring for 12 h under room temperature, volatiles were
removed under vacuum. In a N
2
-
filled glovebox (no exclusion of water), the resulting yellow residue was taken up
in CH
2
Cl
2
(20 mL), washed with saturated aqueous s
olutions of K
2
CO
3
(3 x 10 mL) and NH
4
Cl (3 x 10 mL), dried
over MgSO
4
, and filtered through Celite. The volatiles were removed under reduced pressure. In a glovebox
(exclusion of water and oxygen), the resulting pale
-
yellow solid was dissolved in benzene a
nd filtered through
Celite. The volatile materials were removed once more under vacuum and the resulting mixture was washed by
pentane (3 x 5 mL) and hexanes (3 x 5 mL) and the solid was collected via vacuum filtration, yielding
BINOL
-
(POH)
2
(3.80 g, 44% yield) as a yellow powder.
1
H NMR (400 MHz, C
6
D
6
):
δ
δ
8.33 (d,
J
= 9.7 Hz, 2H, ArH), 7.56 (d,
J
= 7.3 Hz, 2H, ArH), 7.33 (dd,
J
= 8.4,
1.2 Hz, 2H, ArH), 7.09
-
7.04 (m, 4H, ArH), 7.04
6.99 (m, 2H, ArH), 6.93 (ddd,
J
= 8.3, 6.8, 1.4 Hz, 2H,
ArH),
6.60 (s, 2H, ArOH), 6.27 (dd,
J
= 2.8, 1.8 Hz, 4H, ArH), 6.25 (dd,
J
= 2.8, 1.8 Hz, 4H, ArH), 3.13 (s, 18H,
-
OCH
3
);
13
C{
1
H} NMR (101 MHz, C
6
D
6
):
δ
162.96 (d,
J
= 8.6 Hz, 4C, ArC), 162.86 (d,
J
= 8.6 Hz, 4C, ArC), 155.51 (s,
1C, ArC), 155.42 (s, 1C, A
rC), 134.98 (s, 2C, ArC), 134.27 (d,
J
= 27.9 Hz, 2C, ArC), 129.85 (d,
J
= 12.1 Hz, 4C,
ArC), 134.61 (s, 2C, ArC), 129.47 (d,
J
= 2.8 Hz, 2C, ArC), 126.16 (s, 2C, ArC), 125.77 (s, 2C, ArC), 122.97 (s, 2C,
ArC), 114.72 (d,
J
= 45.7 Hz, 2C, ArC), 114.02 (d,
J
= 48.0 Hz, 2C, ArC), 113.74 (s, 2C, ArC), 105.92 (d,
J
= 136.4
Hz, 2C, ArC), 104.85 (s, 4C, ArC), 104.67 (s, 4C, ArC), 55.74 (s, 12C, OCH
3
), 55.62(s, 12C, OCH
3
);
31
P{
1
H} NMR
(121 MHz, C
6
D
6
):
δ
-
54.06 (s,
2P
).
S
4
BINOL
-
(PO
-
Ni)
2
(
or
X
-
Ni
2
)
:
In the glove box, to a solution of Py
2
Ni(CH
2
SiMe
3
)
2
(44 mg, 0.119 mmol) in
benzene (4 ml) in a vial was added a solution of
BINOL
-
(POH)
2
(50.39 mg, 0.0563 mmol) in benzene (8 ml).
The mixture was stirred for 2 h under room temperature, forming a red
-
brown solution. Volatile materials were
removed under vacuum. The residue was
triturated
with pentane (3 x 5 mL), then washed by pen
tane (3 x 5 mL)
and hexanes (3 x 5 mL) and the solid was collected via vacuum filtration, yielding the complex
X
-
Ni
2
(55 mg,
73%) as a brown solid.
1
H NMR (400 MHz, C
6
D
6
):
δ
8.43 (dd,
J
= 4.8, 1.7 Hz, 4H, PhH), 8.31 (d,
J
= 12.0 Hz, 2H, PhH), 7.95 (dd,
J
= 8.6, 1.0 Hz, 2H, PhH), 7.74 (dd,
J
= 8.1, 1.5 Hz, 2H, PhH), 7.21
7.07 (m, 6H, PhH), 6.99 (ddd,
J
= 7.9, 6.5,
1.2 Hz, 2H, PhH), 6.60
6.52 (m, 2H, PhH), 6.34 (dd,
J
= 8.3, 3.5 Hz, 4H, PhH), 6.28 (dd,
J
= 8.3, 3.5 Hz, 4H,
PhH), 6.17 (t,
J
= 7.0 Hz, 4H,
PhH), 3.34 (s, 12H,
-
OCH
3
), 3.19 (s, 12H,
-
OCH
3
),
-
0.17 (s, 18H,
-
Si(CH
3
)
3
),
-
0.59
(t,
J
= 11.7 Hz, 2H,
-
C
H
H'Si(CH
3
)
3
),
-
0.96 (dd,
J
= 12.1, 7.0 Hz, 2H,
-
CH
H'
Si(CH
3
)
3
);
13
C{
1
H} NMR (101 MHz,
C
6
D
6
):
δ
169.14 (d,
J
= 21.2 Hz, 4C, ArC), 162.02 (d,
J
= 29.5 Hz, 8C, ArC), 151.35 (s, 4C, ArC), 137.72 (s, 2C,
ArC), 135.43 (s, 2C, ArC), 134.32 (d,
J
= 52.1 Hz, 2C, ArC), 130.46 (d,
J
= 38.3 Hz, 4C, ArC), 128.66 (d,
J
= 2.8
Hz, 2C, ArC), 128.49 (s, 2C, ArC), 127.94 (s, 2C, ArC), 126.47 (d,
J
= 8.3 Hz, 2C, A
rC), 124.44 (s, 2C, ArC),
122.85 (s, 4C, ArC), 118.28 (s, 2C, ArC), 112.23 (d,
J
= 45.7 Hz, 2C, ArC), 111.60 (d,
J
= 48.0 Hz, 2C, ArC), 105.06
(d,
J
= 4.2 Hz, 4C, ArC), 104.81 (d,
J
= 4.2 Hz, 4C, ArC), 55.57 (s, 4C, OCH
3
), 55.06 (s, 4C, OCH
3
), 2.48 (s, 6C,
SiMe
3
),
-
18.73 (d,
J
= 30.0 Hz, 2C, NiCH
2
Si);
31
P{
1
H} NMR (121 MHz, C
6
D
6
):
δ
-
5.52 (s,
2P
).
Anal. Calcd
(%)
for C
70
H
78
N
2
Ni
2
O
10
P
2
Si
2
: C, 6
2.61
; H, 5
.85
; N,
2.09
. Found(%): C, 6
3.23
; H,
6.05
; N,
2.17
.
S
5
3 Cation
Binding Studies
Procedures:
0.005 mmol of
X
-
Ni
2
prepared using the above procedure was dissolved in C
6
D
6
(0.4 mL). To this
solution was added a certain amount of THF solution of NaBAr
F
24
(0.05 M). The mixture was transferred to
a J
-
Yo un g tu b e wi th a cap il la r y i nser t w i th CD Cl
3
solution of MePPh
3
+
Br
-
inside as an external standard. Spectra
were collected every 10 min on a
Bruker Cryoprobe 400 spectrometer until no further change was observed.
NMR spectra:
Figure S
1
.
31
P{
1
H} NMR spectra of
X
-
Ni
2
and
in
-
situ
mixture of
X
-
Ni2
and
1
equiv. of
NaBAr
F
24
(
The resonance
at ~22 ppm corresponds to
the i
nternal standard in a capillary)
.
X
-
Ni
2
-
4
0
-
3
0
-
2
0
-
1
0
0
1
0
2
0
3
0
4
0
5
0
X
-
Ni
2
+ 1
NaBAr
F
24
S
6
Figure S
2
.
31
P{
1
H} NMR spectra of
in
-
situ
mixture of
X
-
Ni
2
and
1
~
2
equiv. of
NaBAr
F
24
(
The resonance at ~22
ppm corresponds to
the i
nternal standard in a capillary)
.
X
-
Ni
2
+ 1
NaBAr
F
24
X
-
Ni
2
+ 1.5
NaBAr
F
24
X
-
Ni
2
+ 2
NaBAr
F
24
-
5
0
-
4
0
-
3
0
-
2
0
-
1
0
0
1
0
2
0
3
0
4
0
5
0
S
7
Figure S
3
.
31
P{
1
H} NMR spectra of
in
-
situ
mixture of
X
-
Ni
2
and 0~
1
equiv. of
NaBAr
F
24
(The resonance at
~22 ppm corresponds to
the i
nternal standard in a capillary)
.





















X
-
Ni
2
X
-
Ni
2
+ 0.25
NaBAr
F
24
X
-
Ni
2
+ 0.5
NaBAr
F
24
X
-
Ni
2
+ 0.75
NaBAr
F
24
X
-
Ni
2
+ 1
NaBAr
F
24
S
8
4
NMR Spectra
Figure
S
4
.
1
H NMR spectrum of
BINOL
-
(POH)
2
in
C
6
D
6
.
Figure
S
5
.
13
C{
1
H} NMR spectrum of
BINOL
-
(POH)
2
in
C
6
D
6
(*: Et
2
O).
0
.
5
1
.
0
1
.
5
2
.
0
2
.
5
3
.
0
3
.
5
4
.
0
4
.
5
5
.
0
5
.
5
6
.
0
6
.
5
7
.
0
7
.
5
8
.
0
8
.
5
9
.
0
9
.
5
1
0
.
0
2
4
.
8
6
8
.
0
1
1
.
9
7
2
.
3
7
2
.
3
7
4
.
5
3
2
.
1
0
2
.
0
0
1
.
9
1
3
.
1
2
5
6
6
.
2
4
3
6
6
.
2
4
8
1
6
.
2
5
0
6
6
.
2
5
5
2
6
.
2
6
4
3
6
.
2
6
8
9
6
.
2
7
1
4
6
.
2
7
5
6
6
.
6
0
0
5
6
.
9
0
6
6
6
.
9
1
0
0
6
.
9
2
3
4
6
.
9
2
7
4
6
.
9
3
1
1
6
.
9
4
4
5
6
.
9
4
8
2
7
.
0
0
7
2
7
.
0
1
0
5
7
.
0
2
4
3
7
.
0
2
7
6
7
.
0
3
0
7
7
.
0
4
1
4
7
.
0
4
3
8
7
.
0
4
7
8
7
.
0
6
1
9
7
.
0
6
4
3
7
.
0
8
2
3
7
.
0
8
5
1
7
.
3
1
4
9
7
.
3
1
7
9
7
.
3
3
5
9
7
.
3
3
8
7
7
.
5
5
0
8
7
.
5
5
2
6
7
.
5
6
9
1
-
1
0
0
1
0
2
0
3
0
4
0
5
0
6
0
7
0
8
0
9
0
1
0
0
1
1
0
1
2
0
1
3
0
1
4
0
1
5
0
1
6
0
1
7
0
1
8
0
1
9
0
2
0
0
1
0
4
.
3
0
8
1
1
0
4
.
4
9
0
4
1
0
4
.
7
1
2
7
1
0
4
.
8
4
4
0
1
0
4
.
8
7
3
2
1
0
6
.
2
2
9
3
1
1
3
.
3
7
8
4
1
1
3
.
5
3
1
5
1
1
3
.
7
7
9
4
1
1
4
.
2
2
7
9
1
1
4
.
4
7
5
8
1
2
2
.
6
0
5
5
1
2
5
.
4
0
1
7
1
2
5
.
7
9
9
1
1
2
9
.
0
5
4
7
1
2
9
.
1
5
3
1
1
2
9
.
2
4
4
2
1
2
9
.
4
2
2
9
1
2
9
.
5
4
3
2
1
3
3
.
7
6
8
5
1
3
4
.
0
4
5
6
1
3
4
.
6
1
7
9
1
5
5
.
0
5
5
4
1
5
5
.
1
4
2
9
1
6
2
.
4
4
8
7
1
6
2
.
5
3
2
6
1
6
2
.
5
5
0
8
1
6
2
.
6
3
8
3
*
*
S
9
Figure
S
6
.
31
P{
1
H} NMR
spectrum of
BINOL
-
(POH)
2
in
in C
6
D
6
.
Figure
S
7
.
1
H NMR spectrum of
BINOL
-
(PO
-
Ni)
2
(
X
-
Ni
2
)
in
C
6
D
6
.
-
2
4
0
-
2
2
0
-
2
0
0
-
1
8
0
-
1
6
0
-
1
4
0
-
1
2
0
-
1
0
0
-
8
0
-
6
0
-
4
0
-
2
0
0
2
0
4
0
6
0
8
0
1
0
0
1
2
0
1
4
0
-
5
4
.
0
5
8
0
-
2
.
0
-
1
.
5
-
1
.
0
-
0
.
5
0
.
0
0
.
5
1
.
0
1
.
5
2
.
0
2
.
5
3
.
0
3
.
5
4
.
0
4
.
5
5
.
0
5
.
5
6
.
0
6
.
5
7
.
0
7
.
5
8
.
0
8
.
5
9
.
0
9
.
5
1
.
9
6
1
.
9
6
1
8
.
0
0
1
2
.
0
0
1
2
.
0
3
4
.
0
5
4
.
0
8
4
.
0
9
2
.
0
0
2
.
0
9
4
.
3
5
2
.
2
5
2
.
0
0
2
.
0
0
2
.
0
0
4
.
0
0
-
0
.
5
9
4
9
-
0
.
1
6
9
9
3
.
1
9
4
7
3
.
3
3
8
6
6
.
1
4
8
6
6
.
1
6
6
3
6
.
1
8
3
7
6
.
2
6
7
8
6
.
2
7
6
6
6
.
2
8
8
5
6
.
2
9
7
4
6
.
3
2
5
8
6
.
3
3
4
7
6
.
3
4
6
6
6
.
3
5
5
5
6
.
5
5
9
6
6
.
9
8
9
2
6
.
9
9
2
9
7
.
0
8
9
7
7
.
1
1
0
2
7
.
1
2
0
6
7
.
1
3
1
0
7
.
1
4
1
1
7
.
7
3
2
3
7
.
7
3
6
0
7
.
7
5
2
5
7
.
7
5
6
5
7
.
9
3
6
1
7
.
9
3
8
6
7
.
9
5
7
5
7
.
9
6
0
0
8
.
2
9
4
3
8
.
3
2
4
2
8
.
4
2
2
3
8
.
4
2
6
6
8
.
4
3
4
5
8
.
4
3
8
5
S
10
Figure
S
8
.
13
C{
1
H} NMR spectrum of
BINOL
-
(PO
-
Ni)
2
(
X
-
Ni
2
)
in
C
6
D
6
.
Figure
S
9
.
1
H
-
13
C{
1
H} HSQC NMR spectrum of
BINOL
-
(PO
-
Ni)
2
(
X
-
Ni
2
)
in
C
6
D
6
.
-
3
0
-
2
0
-
1
0
0
1
0
2
0
3
0
4
0
5
0
6
0
7
0
8
0
9
0
1
0
0
1
1
0
1
2
0
1
3
0
1
4
0
1
5
0
1
6
0
1
7
0
1
8
0
1
9
0
-
1
8
.
8
8
3
9
-
1
8
.
5
8
5
8
2
.
4
7
5
2
5
5
.
0
5
8
9
5
5
.
5
7
2
6
1
0
4
.
7
9
4
3
1
0
4
.
8
3
5
6
1
0
5
.
0
3
7
4
1
0
5
.
0
7
8
7
1
1
1
.
3
6
2
1
1
1
1
.
8
3
9
1
1
1
2
.
0
0
4
2
1
1
2
.
4
5
8
3
1
1
8
.
2
7
8
5
1
2
2
.
8
4
6
6
1
2
4
.
4
4
2
7
1
2
6
.
4
2
4
0
1
2
6
.
5
0
6
6
1
2
7
.
9
3
7
6
1
2
8
.
4
8
7
9
1
2
8
.
6
4
3
9
1
2
8
.
6
7
1
4
1
3
0
.
2
6
7
5
1
3
0
.
6
4
8
2
1
3
4
.
0
6
0
5
1
3
4
.
5
7
8
7
1
3
5
.
4
3
1
8
1
3
7
.
7
1
5
9
1
5
1
.
3
4
6
8
1
6
1
.
8
7
7
3
1
6
2
.
1
7
0
8
1
6
9
.
0
3
2
2
1
6
9
.
2
4
3
1
6
.
5
7
.
0
7
.
5
8
.
0
8
.
5
9
.
0
1
0
5
1
1
0
1
1
5
1
2
0
1
2
5
1
3
0
1
3
5
1
4
0
1
4
5
1
5
0
S
11
Figure
S
10
.
31
P{
1
H} NMR
spectrum of
BINOL
-
(PO
-
Ni)
2
(
X
-
Ni
2
)
in
in C
6
D
6
.
-
1
5
0
-
1
3
0
-
1
1
0
-
9
0
-
7
0
-
5
0
-
3
0
-
1
0
1
0
3
0
5
0
7
0
9
0
1
1
0
1
3
0
-
5
.
5
2
4
7
S
12
Figure
S1
1
.
31
P{
1
H} NMR spectra of
III
(top)
and
in
-
situ
mixture of
III
and
1
equiv. of
NaBAr
F
24
(bottom).
Solvent: THF
-
H8
.
31
P
chemical shifts were c
alibrated by an external standard
.
The single sharp resonance moves
from
-
4.77 ppm (top) to
-
4.81 ppm (bottom).
MeO
O
P
Br
OMe
MeO
OMe
Ni
py
t
Bu
Me
3
Si
NaBAr
F
24
III
-
2
0
-
1
5
-
1
0
-
5
0
5
S
13
Figure
S12.
31
P{
1
H} NMR spectra of
III
-
tBA
(top) and
in
-
situ
mixture of
III
-
tBA
and
1
equiv. of
NaBAr
F
24
(bottom). Solvent: THF
-
H8.
31
P
chemical shifts were c
alibrated by an external standard. The
two broad
resonance
s at
-
6.14 and
-
3.37 ppm collapsed to one sharper
resonance at
-
5.14 ppm
.
III
-
tBA
was prepared
based on a procedure reported in literature.
NaBAr
F
24
III-tBA
t
Bu
P
O
OMe
OMe
Ni
py
OMe
MeO
Br
O
t
BuO
Me
3
Si
-
2
0
-
1
0
0
1
0