S
1
Supporting Information for
Catalyst Editing via
Post
-
Synthetic
Functionalization by
Phosphonium Generation and Anion Exchange for Nickel
-
Catalyzed Ethylene/Acrylate Copolymerization
Priyabrata Ghana
[a]
,
Shuoyan
Xiong
[a]
,
Adjeoda
Tekpor
[a]
,
Brad C. Bailey
[b]
, Heather A. Spinney
[b]
,
Briana S. Henderson
[b]
,
and 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, United States
b
Chemical Science, Core R&D, The Dow Chemical Company, Midland, Michigan 48667, United States
Experimental details for
1.
General considerations
S2
2.
Preparations of phosphonium ligands
S
3
3.
Preparation of metal complexes
S
11
4.
NMR spectra
S
2
0
5.
Cryst
al
lographic
i
nformation
S
3
2
6.
Topographical
analyses
S
3
4
7
.
Procedures for
polymerization and polymer characterization
S
3
5
8
.
Supplemental data
for
olefin
(
co
)
polymerization
catalysis
S
38
9.
Supplemental data
for
polymer characterization
S
4
2
10
.
References
S
5
1
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
Deuterated solvents were purchased
from Cambridge Isotopes Lab, Inc.; C
6
D
6
and THF
-
d
8
were dried with Na/benzophenone ketyl and vacuum
transferred. ert
-
b
utyl acrylate was dried over 4 Å sieves for greater than 72h.
Methyl iodide, 1
-
bromopenatne, 5
-
bromo
-
1
-
pentene and tert
-
butyl
-
3
-
br
o
mopropionate were purchased from Sigma Aldrich
and dried over 4
Å sieves
for several days before use. 4
-
methylbenzyl bromide, 4
-
triflu
o
romethylbenzyl
bromide and 3,5
-
di
-
tert
-
butylbenzyl bromide were purchased from Sigma Aldrich and used as received.
2,6
-
bis(bis(2,6
-
dimethoxyphenyl)phosph
ino
)
-
4
-
(tert
-
butyl)phenol (
POPH
)
and complex
POP
-
Ni
were
prepared following the earlier reported procedure.
2
S
odium tetrakis
(3,5
-
bis(trifluoromethyl)phenyl)
-
l
4
-
borane (NaBAr
F
2
4
) and the nickel precursor [(py)
2
Ni(CH
2
SiMe
3
)
2
] were prepared following the literature
procedures.
3
,
4
All
1
H,
13
C,
19
F
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 residual solvent resonances.
S
3
2.
Preparation of
Phosphonium Ligands
(
1a
)
To a solution of
POPH
(50 mg, 0.066 mmol) in toluene (5 mL) in a 20 mL
Teflon
-
fitted Schlenk tube
,
a solution of
methyl iodide
(9.35 mg, 0.066 mmol) in toluene (1 mL) was added at
-
78 °C under nitrogen
atmosphere. After addition, the reaction mixture was allowed to warm to room temperature over 1 hour
and stirred additionally for 18 hours. The resulting colorless suspension was evaporated to dryness under
vacuum and the residue was t
reated with NaBAr
F
4
(58.4 mg, 0.066 mmol, 1 equiv.) and fluorobenzene (4
mL) at room temperature and stirred for 2 hours. The suspension was filtered through Celite and the solvent
was removed under va
cuum. The resulting oily residue was
triturated
with
n
-
pentane (2
×
3 mL) and then
dried under reduced pressure to obtain a colorless powder. Yield: 105 mg (0.064 mmol, 97%).
1
H NMR (400.1 MHz, C
6
D
6
):
δ 8.41 (br s, 8H, B(C
6
H
3
-
3,5
-
(CF
3
)
2
)
4
), 8.05 (d,
J
= 9.5 Hz, 1H, ArH), 7.68
(br s, 1H, OH; this signal overlaps with the signal at 7.66 ppm), 7.66 (br s, 4H, B(C
6
H
3
-
3,5
-
(CF
3
)
2
)
4
), 7.05
(t,
J
= 8.3 Hz, 2H, ArH), 7.00 (t,
J
= 8.3 Hz, 2H, ArH), 6.84 (d,
J
= 17.6 Hz,
1H, ArH), 6.21 (dd,
J
= 8.3,
3.1 Hz,
4
H,
Ar
H), 6.00 (dd,
J
= 8.5, 5.2 Hz,
4
H, Ar
H), 3.09 (s, 12H, OCH
3
), 2.81 (s, 12H, OCH
3
), 2.29 (d,
J
= 15.2 Hz,
3H, PCH
3
), 1.02 (s, 9H, C(CH
3
)
3
).
31
P
{
1
H}
NMR (161.97 MHz, C
6
D
6
): 8.4 (d
,
J
= 4.5 Hz
),
-
62.3 (br s).
S
4
(
1b
)
In a N
2
-
filled glovebox, a solution
of 1
-
bromopentane (30 mg, 0.20 mmol, 3 equiv.) in toluene (3 mL)
was added
t
o a solution of
POPH
(50 mg, 0.066 mmol) in toluene
-
fluorobenzene mixture (5+5 mL) in a
20 mL
scintillation
vial
at room temperature. After addition, the reaction mixture was stirred for 7 days for
completion of the reaction. The resulting colorless suspension was evaporated to dryness under vacuum
and the residue was
triturated
with hexane (3 mL) followed by toluene (3 mL) and the dried under reduced
pressure to obtain a colorless solid (54 mg, 0.059 mmol). The resulting solid was treated with NaBAr
F
4
(52.6
mg, 0.059 mmol, 1 e
quiv.) and fluorobenzene (5 mL) at room temperature and stirred for 2 hours. The
suspension was filtered through Celite and the volatile materials of the filtrate were removed under vacuum.
The resulting oily residue was
triturated
with
n
-
pentane (2×3 mL) and then dried under reduced pressure
for 3 hours to obtain a colorless powder. Overall yield: 92 mg (0.054 mmol, 82%).
1
H NMR (400.1 MHz, C
6
D
6
):
δ 8.41 (br s, 8H, B(C
6
H
3
-
3,5
-
(CF
3
)
2
)
4
), 7.91 (ddd,
J
= 7.3, 2.3, 0.8 Hz, 1H,
ArH), 7.87 (br
s, 1H, OH), 7.67 (br s, 4H, B(C
6
H
3
-
3,5
-
(CF
3
)
2
)
4
), 7.05 (t,
J
= 8.2 Hz, 2H, ArH), 7.00 (t,
J
=
8.4 Hz, 2H, ArH), 6.84 (dd,
J
= 16.9, 2.4 Hz,
1H, ArH), 6.21 (dd,
J
= 8.3, 3.2 Hz,
4
H, Ar
H), 6.01 (dd,
J
=
8.4, 5.0 Hz,
4
H, Ar
H), 3.10 (s, 12H, OCH
3
), 2.89 (s, 12H, OCH
3
), 2.86 (br m, 2H, PCH
2
), 1.11 (m, 4H,
CH
2
; two
CH2
signals
overlap with each other), 1.00 (s, 9H, C(CH
3
)
3
), 0.77 (t,
J
= 7.0 Hz, 3H, CH
3
).
31
P
{
1
H}
NMR (161.97 MHz,
C
6
D
6
): 15.7 (d,
J
= 7.8 Hz),
-
65.3 (br s).
S
5
(
1c
)
In a N
2
-
filled glovebox,
a solution of 5
-
bromo
-
1
-
pentene (11.8 mg, 0.0.079 mmol, 1 equiv.) in toluene (1
mL) was added
t
o a solution of
POPH
(60 mg, 0.079 mmol) in toluene (8 mL) in a 20 mL
scintillation
vial
at room temperature. After addition, the reaction mixture was stirred for 2 weeks for completion of the
reaction. The resulting colorless suspension was evaporated to dryness under vacuum and the residue was
triturated
with
n
-
pentane (2
×
5 mL) and the dried under reduced pressure to obtain a colorless solid. The
resulting solid was treated with NaBAr
F
4
(70 mg, 0.079 mmol, 1 equiv.) and fluorobenzene (5 mL) at room
temperature and stirred f
or 3 hours. The suspension was filtered through Celite and the volatile materials
of the filtrate were removed under vacuum. The resulting foamy residue was
triturated
with
n
-
pentane (2
×
3 mL) and then dried under reduced pressure for 4 hours to obtain a colorless powder. Overall yield: 110
mg (0.065 mmol, 82%).
1
H NMR (400.1 MHz, C
6
D
6
):
δ 8.41 (br s, 8H, B(C
6
H
3
-
3,5
-
(CF
3
)
2
)
4
), 7.93 (ddd,
J
= 7.8, 2.4, 0.9 Hz, 1H,
ArH), 7.88 (br s, 1H, OH), 7.66 (br s, 4H, B(C
6
H
3
-
3,5
-
(CF
3
)
2
)
4
), 7.05 (t,
J
= 8.2 Hz, 2H, ArH), 6.98 (t,
J
=
8.4 Hz, 2H, ArH), 6.83 (dd,
J
= 16.8, 2.4 Hz,
1H, ArH), 6.21 (dd,
J
= 8.3, 3.1 Hz,
4
H, Ar
H), 5.99 (dd,
J
=
8.5, 5.1 Hz,
4
H, Ar
H), 5.51 (m, 1H, CH
2
=C
H
), 4.90 (m, 2H, C
H
2
=CH), 3.09 (s, 12H, OCH
3
), 2.94 (br m,
2H, PCH
2
), 2.86 (s, 12H, OCH
3
), 1.86 (brq,
J
= 7.1 Hz,
2H, CH
2
), 1.27 (m, 2H, CH
2
), 1.00 (s, 9H, C(CH
3
)
3
).
31
P
{
1
H}
NMR (161.97 MHz,
C
6
D
6
): 15.7 (d,
J
= 6.9 Hz),
-
64.7 (br s).
S
6
(
1d
)
In a N
2
-
filled glovebox, a solution of tert
-
butyl 3
-
bromopropanoate (15.4 mg, 0.074 mmol) in benzene
(1 mL) was added to a solution of
POPH
(56 mg, 0.074 mmol) in benzene (3 mL) in a 20 mL scintillation
vial at room temperature. The resulting solution was stirred at room temperature for 16 hours, leading to a
colorless suspension. After completion of the reaction, all the volatiles were remove
d under reduced
pressure. The resulting residue was washed with
n
-
pentane (2
× 3 mL) and then dried under vacuum for 2
hour
s. The obtained white solid was dissolved in fluorobenzene (5 mL) and to this solution, a fluorobenzene
solution (2 mL) of NaBAr
F
4
(65.4 mg, 0.074 mmol, 1 equiv.) was added and stirred for 16 hours at room
temperature. The resulting colorless suspension was filtered through Celite and the filtrate was evaporated
to dryness under reduced pressure. The oily residue was
triturated with
n
-
pentane (2
× 5 mL) and dried
under vacuum for 30 minutes to obtain the desired phosphonium salt as a white powder. Yield: 71
mg
(0.073 mmol, 99%).
1
H NMR (400.1 MHz, C
6
D
6
):
δ 8.41 (br s, 8H, B(C
6
H
3
-
3,5
-
(CF
3
)
2
)
4
), 8.04
–
7.97 (ddd + br s, 2H, J = 8.8,
2.4, 0.9 Hz,ArH + OH; two signals overlap with each other), 7.67 (br s, 4H, B(C
6
H
3
-
3,5
-
(CF
3
)
2
)
4
), 7.06 (t,
J
= 8.3 Hz, 2H, ArH), 6.98 (t,
J
= 8.3 Hz, 2H, ArH), 6.85 (dd,
J
= 17.1, 2.4 Hz, 1H, ArH), 6.24 (dd,
J
= 8.3,
3.2 Hz, 4
H, Ar
H), 5.98 (dd,
J
= 8.5, 5.2 Hz, 4H
,
ArH), 3.43 (m, 2H, CH
2
), 3.13 (s, 12H, OCH
3
), 2.86 (s,
12H, OCH
3
), 2.35 (m, 2H, CH
2
), 1.31 (s, 9H, C(CH
3
)
3
), 1.01 (s, 9H, C(CH
3
)
3
).
31
P{
1
H} NMR (161.97 MHz, C
6
D
6
): 15.2 (d,
J
= 5.9 Hz),
-
64.1 (br s).
S
7
(
1e
)
In a N
2
-
filled glovebox, a solution of
4
-
methylbenzyl bromide (15.8 mg, 0.085 mmol, 1 equiv.) in
benzene
(1 mL)
was added t
o a solution of
POPH
(65 mg, 0.085 mmol) in benzene (8 mL)
in a 20 mL
scintillation
vial
at room temperature. The resulting colorless solution was stirred for 18 hours at room temperature,
yielding a colorless suspension. After completion of the reaction, all the volatiles were removed under
reduced pressure. The resulting residue was treated
with NaBAr
F
4
(75.9 mg, 0.085 mmol, 1 equiv.) and
fluorobenzene (6 mL) at room temperature and stirred for 3 hours. The colorless suspension wa
s filtered
through Celite and the filtrate was evaporated under reduced pressure. The oily, colorless residue was
triturated
with
n
-
pentane (2 × 3 mL) and dried under vacuum for 3 hours to obtain a white powder. Yield:
142 mg (0.082 mmol, 97%).
1
H NMR (400.1 MHz, C
6
D
6
):
δ 8.42 (br s, 8H, B(C
6
H
3
-
3,5
-
(CF
3
)
2
)
4
), 7.86 (br s, 1H, OH), 7.80 (ddd,
J
=
7.9, 2.4, 0.8 Hz, 1H, ArH), 7.66 (br s, 4H, B(C
6
H
3
-
3,5
-
(CF
3
)
2
)
4
), 7.04 (td,
J
= 8.3, 0.7 Hz, 2H, ArH), 6.95 (t,
J
= 8.4 Hz, 2H, ArH), 6.88 (dd,
J
= 16.4, 2.4 Hz, 1H, ArH), 6.66 (dd,
J
= 8.2, 2.1 Hz, 2H, ArH), 6.51(d,
J
= 7.9 Hz, 2H, ArH), 6.20 (dd,
J
= 8.4, 3.1 Hz, 4
H, Ar
H), 5.97 (dd,
J
= 8.4, 5.2 Hz, 4
H, Ar
H), 4.47 (d,
J
=
17.1 Hz, 2H, CH
2
Ar), 3.04 (s, 12H, OCH
3
), 2.90 (s, 12H, OCH
3
), 1.91 (d,
J
= 1.9 Hz, 3H, PhCH
3
), 0.99 (s,
9H, C(CH
3
)
3
).
31
P
{
1
H}
NMR (161.97 MHz,
C
6
D
6
): 14.6 (d,
J
= 6.8 Hz),
-
64.2 (br s).
S
8
(
1f
)
In a N
2
-
filled glovebox, a
solid mixture of
POPH
(50 mg, 0.066 mmol) and 1
-
(bromomethyl)
-
4
-
(trifluoromethyl)benzene (15.7 mg, 0.066 mmol, 1 equiv.) in a 20 mL
scintillation
vial was treated with
toluene (5 mL) at room temperature. The resulting colorless solution was stirred for 18 hours at room
temperature, yielding a colorless suspension. After completion of the reaction, all the volatiles were
removed under reduced pressu
re. The resulting residue was treated with NaBAr
F
4
(58.4 mg, 0.066 mmol,
1 equiv.) and fluorobenzene (5mL) at room temperature and s
tirred for 4 hours. The colorless suspension
was filtered through Celite and the filtrate was evaporated under reduced pressure. The oily, colorless
residue was
triturated
with
n
-
pentane (2 × 5 mL) and the then dried under vacuum for 2 hours to obtain a
white powder. Yield: 108 mg (0.061 mmol, 92%).
1
H NMR (400.1 MHz, C
6
D
6
):
δ 8.41 (br s, 8H, B(C
6
H
3
-
3,5
-
(CF
3
)
2
)
4
), 7.86 (br s, 1H, OH), 7.65 (br s,
(4+1)H, B(C
6
H
3
-
3,5
-
(CF
3
)
2
)
4
+ ArH; two signals overlap with each other), 7.06 (t,
J
= 8.4 Hz,
2H, ArH
),
6.98 (t,
J
= 8.4 Hz,
2H, ArH), 6.76 (d,
J
= 8.0 Hz,
2H, ArH), 6.69 (d,
J
= 8.0 Hz,
2H, ArH), 6.64 (d,
J
= 16.9
Hz,
1H, ArH), 6.22 (dd,
J
= 8.2, 3.2 Hz,
4
H, Ar
H), 6.00 (dd,
J
= 8.4, 5.2 Hz,
4
H, Ar
H), 4.44 (d,
J
= 17.8 Hz,
2H, CH
2
Ar), 3.06 (s, 12H, OCH
3
), 2.96 (s, 12H, OCH
3
), 0.90 (s, 9H, C(CH
3
)
3
)
.
31
P
{
1
H}
NMR (161.97 MHz, C
6
D
6
): 14.6 (d,
J
= 8.6 Hz),
-
65.3 (brs).
19
F NMR (376.16 MHz, C
6
D
6
):
-
62.24 (s, 24F),
-
62.47 (s, 3F).
S
9
(
1g
)
In a N2
-
filled glovebox, a solution of
1
-
(bromomethyl)
-
3,5
-
di
-
tert
-
butylbenzene (18.7 mg, 0.066 mmol,
1 equiv.) in benzene (1 mL) was added
t
o a solution of
POPH
(50 mg, 0.066 mmol) in benzene (4 mL)
in
a 20 mL glass vial
at room temperature. The resulting colorless solution was stirred for 16 hours at room
temperature, yielding a colorless suspension. After completion of the reaction, solvent was removed under
reduced pressure. The resulting residue was treated with NaBAr
F
4
(58.4 mg, 0.066 mmol, 1 equiv.) a
nd
fluorobenzene (5mL) at room temperature and stirred for 3 hours. The colorless suspension was filtered
through Celite and the filtrate was evaporated to dryness. The oily residue was
triturated
with
n
-
pentane (2
× 5 mL) and dried under vacuum for 2 hours to obtain a white powder. Yield: 107 mg (0.059 mmol, 89%).
1
H NMR (400.1 MHz, C
6
D
6
):
δ 8.42 (br s, 8H, B(C
6
H
3
-
3,5
-
(CF
3
)
2
)
4
), 8.00 (br s, 1H, OH), 7.97 (d,
J
= 9.2
Hz, 1H, ArH), 7.69 (br s, 4H, B(C
6
H
3
-
3,5
-
(CF
3
)
2
)
4
), 7.21 (s, 1H, ArH
), 7.16 (d, 1H, ArH; this signal overlaps
with the C
6
D
5
H signal), 7.02 (t,
J
= 8.6 Hz, 2H, ArH), 6.96 (t,
J
= 8.6 Hz, 2H, ArH), 6.83 (s, 2H, ArH), 6.19
(dd, 4
H, Ar
H), 6.00 (dd, 4
H, Ar
H), 4.51 (d,
J
= 16.8 Hz, 2H, CH
2
Ar), 3.04 (s, 12H, OCH
3
), 2.87 (s, 12H,
OCH
3
), 1.12 (s, 18H, C(CH
3
)
3
) 1.11 (s, 9H, C(CH
3
)
3
; this signal overlaps with the signal at 1.12 ppm).
31
P
{
1
H}
NMR (161.97 MHz, C
6
D
6
): 13.3 (br s),
-
60.1 (br s).
S
10
(
1a'
)
In a N
2
-
filled glovebox, a solution of methyl
iodide (37 mg, 0.26 mmol, 1 equiv.) in toluene (0.5 mL) was
added
t
o a solution of
POPH
(200 mg, 0.26 mmol, 1 equiv.) in toluene (20 mL) in a
60 mL glass jar
at
-
78
°C. The reaction was stirred
at
-
78 °C for 15
minutes and allowed to come to room temperature slowly.
The reaction mixture was stirred at room temperature for 18 hr, forming a white precipitate. The mixture
was filtered over a glass fritted funnel and the solid
residue was
washed with toluene (3×10 mL), followed
by n
-
pentane (3
×
2 mL). The
resulting
solid was dried in
vacuo
for 30 minutes and collected as a white
powder (192 mg, 0.21 mmol). In a 20 mL scintillation vial a part of the isolated solid (50 mg, 0.06 mmol)
and sodium triflate (9.5 mg, 0.06
mmol, 1 equiv.) were suspended in fluorobenzene
(
4 mL
)
, forming a turbid
off
-
white solution. The reaction mixture was stirred for 72 hours at room temperature and filtered through
Celite to yield a clear, colorless solution. All the volatiles were removed, the residue was washed with
n
-
pentane (3
×
2 mL) and dried under
reduced pressure
to afford
1
a'
as a white powder(44 mg, 85%).
1
H NMR (400 MHz, C
6
D
6
/C
6
H
5
F): 6.39 (dd, J
HH
= 8.3, 5.2 Hz, 4H, ArH), 6.33 (dd, J
HH
= 8.3, 3.1 Hz,
4H, ArH), 3.20 (s, 12H, OCH
3
), 3.16 (s, 12H, OCH
3
), 2.64 (d, J
HP
= 15.5 Hz, 3H, PCH
3
), 1.05 (s, 9H,
C(CH
3
)
3
).
31
P
{
1
H}
NMR (162 MHz, C
6
D
6
/C
6
H
5
F): 8.71 (brs),
-
60.69 (br s)
19
F NMR (376 MHz, C
6
D
6
/C
6
H
5
F):
-
77.74 (s, CF
3
)
S
11
3
.
Preparation of
Metal Complexes
(
2a
)
In a N
2
-
filled glovebox,
a dark orange solution of [
(py)
2
Ni(CH
2
SiMe
3
)
2
] (25.1 mg, 0.064 mmol, 1 equiv.)
in THF (2 mL) was added
t
o acolorless
solutionof
1a
(105 mg, 0.064 mmol) in THF (3 mL) in a 20 mL
scintillation
vialat room temperature. The resulting mixture was stirred for 20 minutes, leading to a light
orange solution. All the volatiles were removed under reduced pressure and the residue was washed with
n
-
pentane (2
× 2 mL). The resulting oily residue was extracted with benzene (15 mL) at room temperature
and dried under vacuum to obtain the product as an orange powder. Yield: 112 mg (0.060 mmol, 94%).
1
H NMR (400.1 MHz, THF
-
d
8
):
δ 8.73 (d,
J
= 4.2 Hz, 2H, py), 7.81 (br s, (8+1)H, B(C
6
H
3
-
3,5
-
(CF
3
)
2
)
4
+
ArH; two signals overlap with each other), 7.69 (t,
J
= 7.4 Hz, 1H, py), 7.59 (br s, 4H, B(C
6
H
3
-
3,5
-
(CF
3
)
2
)
4
),
7.57 (t,
J
= 8.3 Hz, 2H, ArH
; this signal partially overlaps with the signal at 7.59 ppm), 7.35 (t,
J
= 8.3 Hz,
2H, ArH), 7.03 (t,
J
= 6.4 Hz, 2H, py), 6.75 (dd,
J
= 8.2, 4.9 Hz, 4H, ArH), 6.67 (dd,
J
= 8.2, 3.2 Hz, 4H,
ArH), 6.63 (d, 1H, ArH; this signal partially overlaps with the signal at 6.67), 3.67 (s, 12H, OCH
3
), 3.63 (s,
12H, OCH
3
), 2.38 (d,
J
= 15.7 Hz, 3H, PCH
3
), 1.02 (s, 9H, C(CH
3
)
3
),
-
0.57 (s, 9H, SiMe
3
),
-
0.83 (d,
J
= 9.2
Hz, 2H, NiCH
2
).
13
C
{
1
H}
NMR (101 MHz, THF
-
d
8
):
δ 173.95 (dd,
J
CP
= 25.0, 5.6 Hz, Ar
-
C)), 163.94 (s,
Ar
-
C), 162.80 (q,
J
CF
= 50.0 Hz, Ar
F
-
C), 162.07 (d,
J
CP
= 1.3 Hz, Ar
-
C), 151.67 (s, py), 137.97 (s, py), 136.29
(s, Ar
-
C), 135.59 (s, Ar
F
-
C), 135.16 (dd,
J
CP
= 13.2, 6.2 Hz, Ar
-
C), 134.3 (t,
J
CP
= 2.5 Hz, Ar
-
C), 131.93 (s,
Ar
-
C), 130.83 (dd,
J
CP
= 11.3, 1.2 Hz, Ar
-
C), 130.02 (qq,
J
CF
= 31.5, 2.8 Hz, Ar
F
-
C), 128.46 (dd,
J
CP
= 50.5,
8.4 Hz, Ar
-
C), 125.51 (q,
J
CF
= 272.0 Hz, CF
3
), 124.62 (d,
J
CP
= 1.2 Hz, Ar
-
C), 118.18 (sept,
J
CF
= 3.8 Hz,
Ar
F
-
C), 109.96 (d,
J
CP
= 50.1 Hz, Ar
-
C), 107.06 (dd,
J
CP
= 99.8, 10.6 Hz, Ar
-
C), 105.66 (d,
J
CP
= 6.2 Hz, Ar
-
C), 105.36 (d,
J
CP
= 4.3 Hz, Ar
-
C), 101.47 (d,
J
CP
= 95.4 Hz, Ar
-
C), 56.40 (s, OCH
3
), 55.88 (s, OCH
3
), 34.38
(s,
C
(CH
3
)
3
), 31.91 (s, C(
C
H
3
)
3
), 13.81 (d,
J
CP
= 64.1 Hz, P
-
CH
3
), 1.92 (s, Si(CH
3
)
3
),
-
16.43 (d,
J
CP
= 29.4
Hz, SiCH
2
).
31
P
{
1
H}
NMR (161.97 MHz,
THF
-
d
8
):
δ
8.03 (d),
-
7.04 (d).
Anal. Calcd
(%) for
C
84
H
78
BF
24
NNiO
9
P
2
Si: C,
54.21
; H,
4.22
; N,
0.75
. Found(%): C,
54.56
; H,
4.25
; N,
0.61
.
S
12
(
2b
)
In a N
2
-
filled glovebox
,
a dark orange solution of [(py)
2
Ni(CH
2
SiMe
3
)
2
] (20.1 mg, 0.051 mmol, 1 equiv.)
in benzene (5 mL) was added
t
o a
colorless
solution
of
1b
(87 mg, 0.051 mmol) in benzene (10 mL) in a 20
mL
scintillation
vial at room temperature. The resulting mixture was stirred for 30 minutes, leading to a
light orange solution. All the volatiles were removed under reduced pressure and the residue was
triturated
with
n
-
pentane (2
× 5 mL). The resulting orange residue was extracted with benzene (15 mL) at room
temperature and dried under vacuum to obtain the product as an orange powder. Yield: 90 mg (0.047 mmol,
92%).
1
H NMR (400.1 MHz, THF
-
d
8
):
δ 8.71 (m,2H, py), 7.83 (dd, ArH; a part of this signal overlaps with the
signal at 7.81 ppm), 7.81 (brm, 8H, B(C
6
H
3
-
3,5
-
(CF
3
)
2
)
4
), 7.71 (tt,
J
= 7.6, 1.6 Hz, 1H, py), 7.58 (br s, 4H,
B(C
6
H
3
-
3,5
-
(CF
3
)
2
)
4
), 7.55 (t,
J
= 8.4 Hz, 2H, ArH
; this signal partially overlaps with the signal at 7.58 ppm),
7.36 (t,
J
= 8.3 Hz, 2H, ArH), 7.04 (brt,
J
= 6.8 Hz, 2H, py), 6.73 (dd,
J
= 8.4, 4.7 Hz, 4H, ArH), 6.66 (dd,
J
= 8.4, 3.7 Hz, 4H, ArH), 6.62 (ddd,
J
= 17.5, 2.4, 0.8 Hz, 1H, ArH; this signal partially overlaps with the
signal at 6.66), 3.62 (s, 12H, OCH
3
), 3.61 (s, 12H, OCH
3
), 2.73 (m, 2H, PCH
2
), 1.35 (m, 2H, CH
2
), 1.23(m,
4H, CH
2
), 1.04 (s, 9H, C(CH
3
)
3
), 0.87 (m, 2H, CH
3
),
-
0.48 (s, 9H, SiMe
3
),
-
0.83 (d,
J
= 9.2 Hz, 2H, NiCH
2
).
13
C
{
1
H}
NMR (101 MHz, THF
-
d
8
):
δ 174.42 (dd,
J
CP
= 25.0, 5.5 Hz, Ar
-
C)), 163.91 (s, Ar
-
C), 162.81 (q,
J
CF
= 50.0 Hz, Ar
F
-
C), 162.11 (d,
J
CP
= 1.6 Hz, Ar
-
C), 151.66 (s, py), 137.95 (s, py), 136.03 (s, Ar
-
C), 135.59
(s, Ar
F
-
C), 135.14 (dd,
J
CP
= 12.9, 6.2 Hz, Ar
-
C), 134.46 (t,
J
CP
= 2.5 Hz, Ar
-
C), 132.07 (s, Ar
-
C), 131.88
(dd,
J
CP
= 9.8, 1.8 Hz, Ar
-
C), 130.02 (qq,
J
CF
= 31.5, 2.8 Hz, Ar
F
-
C), 127.65 (dd,
J
CP
= 51.5, 8.3 Hz, Ar
-
C),
125.50 (q,
J
CF
= 272.0 Hz, CF
3
), 124.63 (d,
J
CP
= 1.7 Hz, Ar
-
C), 118.18 (sept,
J
CF
= 3.8 Hz, Ar
F
-
C), 109.67
(d,
J
CP
= 49.5 Hz, Ar
-
C), 105.51 (d,
J
CP
= 6.3 Hz, Ar
-
C), 105.25 (d,
J
CP
= 4.2 Hz, Ar
-
C), 104.59 (dd,
J
CP
=
96.6, 10.7 Hz, Ar
-
C), 101.55 (d,
J
CP
= 92.1 Hz, Ar
-
C), 56.24 (s, OCH
3
), 55.88 (s, OCH
3
),34.77 (d,
J
CP
= 20.2
Hz, CH
2
), 34.42 (s,
C
(CH
3
)
3
), 31.96 (s, C(
C
H
3
)
3
), 27.51 (d,
J
CP
= 56.8 Hz, P
-
CH
2
),24.51 (d,
J
CP
= 3.5 Hz,
CH
2
),23.29 (d,
J
CP
= 1.5 Hz, CH
2
), 14.56 (s, CH
3
),2.30 (s, Si(CH
3
)
3
),
-
17.14 (d,
J
CP
= 29.4 Hz, SiCH
2
).
S
13
31
P
{
1
H}
NMR (161.97 MHz,
THF
-
d
8
):
δ
14.55 (d,
J
= 12.3 Hz),
-
7.64 (d,
J
= 12.3 Hz).
Anal. Calcd
(%) for
C
8
8
H
86
BF
24
NNiO
9
P
2
Si: C,
55.13
; H,
4.5
3
; N,
0.7
3
. Found(%): C,
54.5
9
; H,
4.
38
; N,
0.
57
.
(
2c
)
In a N
2
-
filled glovebox,
a dark orange solution of [(py)
2
Ni(CH
2
SiMe
3
)
2
] (25.5 mg, 0.065 mmol, 1 equiv.)
in benzene (4 mL) was added
t
o a
colorless
suspension
of
1c
(110 mg, 0.065 mmol) in benzene (8 mL) in a
20 mL
scintillation
vial
at room temperature. The resulting mixture was stirred for 30 minutes, leading to a
light orange solution. All the volatiles were removed under reduced pressure and the residue was
triturated
with
n
-
pentane (2
× 3 mL) and dried under reduced pressure for 3 hours to obtain an
o
range solid. Yield:
113 mg (0.059 mmol, 91%).
1
H NMR (400.1 MHz, THF
-
d
8
):
δ 8.73 (m,2H, py), 7.85 (br d,
J
= 11.3 Hz, 1H, ArH),7.81 (br s, 8H,
B(C
6
H
3
-
3,5
-
(CF
3
)
2
)
4
), 7.71 (t,
J
= 7.6 Hz, 1H, py), 7.59 (br s, 4H, B(C
6
H
3
-
3,5
-
(CF
3
)
2
)
4
), 7.55 (t,
J
= 8.3 Hz,
2H, ArH), 7.36 (t,
J
= 8.3 Hz, 2H, ArH), 7.04 (t,
J
= 6.7 Hz, 2H, py), 6.73 (dd,
J
= 8.4, 4.8 Hz, 4H, ArH),
6.67 (dd,
J
= 8.3, 3.7 Hz, 4H, ArH), 6.62 (dd,
J
= 15.8, 1.8 Hz, 1H, ArH; this signal partially overlaps with
the signal at 6.67) 5.71 (m, 1H, CH
2
=C
H
), 4.90 (m, 2H, C
H
2
=CH), 3.63 (s, 24H, OCH
3
; two signals overlap
with each other), 2.73 (m, 2H, PCH
2
), 2.03 (q,
J
= 6.9 Hz, CH
2
), 1.44 (m, 2H, CH
2
), 1.04 (s, 9H, C(CH
3
)
3
),
-
0.48 (s, 9H, SiMe
3
),
-
0.81 (d,
J
= 9.2 Hz, 2H, NiCH
2
).
13
C
{
1
H}
NMR (101 MHz, THF
-
d
8
):
δ 174.41 (dd,
J
CP
= 25.1, 5.6 Hz, Ar
-
C), 163.89 (s, Ar
-
C), 162.81 (q,
J
CF
= 50.0 Hz, Ar
F
-
C), 162.09 (d,
J
CP
= 1.3 Hz, Ar
-
C), 151.67 (s, py), 138.75 (s, CH
2
=
C
H), 137.98 (s, py), 136.07 (s, Ar
-
C), 135.58 (s, Ar
F
-
C), 135.23 (dd,
J
CP
=
12.8, 6.1 Hz, Ar
-
C), 134.64 (br s, Ar
-
C), 132.06 (s, Ar
-
C), 130.83 (d,
J
CP
= 11.4 Hz, Ar
-
C), 130.02 (qq,
J
CF
= 31.5, 2.8 Hz, Ar
F
-
C), 127.65 (dd,
J
CP
= 51.4, 8.6 Hz, Ar
-
C), 125.50 (q,
J
CF
= 272.0 Hz, CF
3
), 124.65 (s,
py), 124.15 (s, Ar
-
C), 118.18 (sept,
J
CF
= 3.8 Hz, Ar
F
-
C), 115.71(s,
C
H
2
=CH),109.67 (d,
J
CP
= 49.4 Hz, Ar
-
C), 105.55 (d,
J
CP
= 6.2 Hz, Ar
-
C), 105.27 (d,
J
CP
= 4.1 Hz, Ar
-
C), 104.52 (dd,
J
CP
= 96.4, 9.8Hz, Ar
-
C),
101.55 (d,
J
CP
= 94.4 Hz, Ar
-
C), 56.29 (s, OCH
3
), 55.90 (s, OCH
3
), 36.36 (d,
J
CP
= 20.9 Hz, CH
2
), 34.42 (s,
S
14
C
(CH
3
)
3
), 31.94 (s, C(
C
H
3
)
3
), 27.30 (d,
J
CP
= 57.7 Hz, P
-
CH
2
), 24.03 (s, CH
2
),2.28 (s, Si(CH
3
)
3
),
-
17.06 (d,
J
CP
= 29.4 Hz, SiCH
2
).
31
P
{
1
H}
NMR (161.97 MHz,
THF
-
d
8
):
δ
14.58 (d,
J
= 11.8 Hz),
-
7.66 (d,
J
= 11.8
Hz).
Anal.
Calcd
(%) for C
88
H
84
BF
24
NNiO
9
P
2
Si: C,
55.1
9
; H,
4.
42
; N,
0.73
. Found(%): C,
54.
20
; H,
4.3
0
; N,
0.
50
.
(
2d
)
In a N
2
-
filled glovebox,
a dark orange solution of [(py)
2
Ni(CH
2
SiMe
3
)
2
] (28.8 mg, 0.074 mmol, 1 equiv.)
in
benzene (2 mL) was added
t
o a
colorless
solution
of
1d
(129 mg, 0.074 mmol) ) in benzene (3 mL) in a
20 mL
scintillation
vial at room temperature. The resulting solution was stirred for 30 minutes, leading to
a light orange solution. After completion of the reaction, the solution was treated with
n
-
pentane (1 mL)
and then filtered through Celite. All the volatiles of the orange filtrate were removed under reduced pressure
and the residue was washed with
n
-
pentane (3
× 3 mL). The resulting residue was dried
under vacuum for
1 hour to obtain the product as an orange powder Yield: 112 mg (0.065 mmol, 88%).
1
H NMR (400.1 MHz, THF
-
d
8
):
δ 8.76 (m, 2H, py), 7.87 (dq,
J
= 11.1, 1.2 Hz, 1H, ArH), 7.81 (br s, 8H,
B(C
6
H
3
-
3,5
-
(CF
3
)
2
)
4
), 7.71 (t,
J
= 7.6 Hz, 1H, py), 7.59 (br s, 4H, B(C
6
H
3
-
3,5
-
(CF
3
)
2
)
4
), 7.54 (t,
J
= 8.4 Hz,
2H, ArH), 7.36 (t,
J
= 8.3 Hz, 2H, ArH), 7.11 (t,
J
= 6.7 Hz, 2H, py), 6.71 (dd,
J
= 8.4, 4.9 Hz, 4H, ArH),
6.67 (dd,
J
= 8.3, 3.7 Hz, 4H, ArH), 6.60 (dd,
J
= 17.6, 1.6 Hz,1H, ArH), 3.65 (s, 12H, OCH
3
), 3.59 (s, 12H,
OCH
3
; this signal overlaps with one of the signals of THF
-
d
8
), 3.02 (m, 2H, PCH
2
), 2.42 (m, 2H, CH
2
), 1.48
(s, 9H, C(CH
3
)
3
), 1.04 (s, 9H, C(CH
3
)
3
),
-
0.53 (s, 9H, SiMe
3
),
-
0.80 (d,
J
= 9.3 Hz, 2H, NiCH
2
).
13
C
{
1
H}
NMR (101 MHz, THF
-
d
8
):
δ 174.37 (dd,
J
CP
= 25.0, 5.4 Hz, Ar
-
C)), 172.52 (d,
J
CP
= 1.5 Hz, C=O), 163.82
(s, Ar
-
C), 162.80 (q,
J
CF
= 50.0 Hz, Ar
F
-
C), 162.05 (d,
J
CP
= 1.5 Hz, Ar
-
C), 151.51 (s, py), 137.96 (s, py),
136.23 (s, Ar
-
C), 135.73 (d,
J
CP
= 6.2 Hz, Ar
-
C), 135.58 (s, Ar
F
-
C), 134.84 (t,
J
CP
= 2.5 Hz, Ar
-
C), 132.09 (s,
Ar
-
C), 131.69 (dd,
J
CP
= 10.4, 1.8 Hz, Ar
-
C), 130.01 (qq,
J
CF
= 31.5, 2.9 Hz, Ar
F
-
C), 129.01 (s, Ar
-
C), 128.19
S
15
(d,
J
CP
= 8.2 Hz, Ar
-
C), 127.69 (d,
J
CP
= 8.2 Hz, Ar
-
C), 125.50 (q,
J
CF
= 272.5 Hz, CF
3
), 124.83 (s, Ar
-
C),
118.17 (sept,
J
CF
= 4.0 Hz, Ar
F
-
C), 109.43 (d,
J
CP
= 49.7 Hz, Ar
-
C), 105.61 (d,
J
CP
= 4.3 Hz, Ar
-
C), 105.15
(d,
J
CP
= 4.3 Hz, Ar
-
C), 102.79 (dd,
J
CP
= 96.9, 10.7 Hz, Ar
-
C), 99.68 (d,
J
CP
= 94.4 Hz, Ar
-
C), 79.90 (s,
CH
2
), 55.03 (s, OCH
3
), 54.57 (s, OCH
3
), 33.15 (s,
C
(CH
3
)
3
), 30.60 (s, C(
C
H
3
)
3
), 29.14 (s,
C
(CH
3
)
3
), 27.03 (s,
C(
C
H
3
)
3
), 22.18 (d,
J
CP
= 63.2 Hz, P
-
CH
2
), 0.90 (s, Si(CH
3
)
3
),
-
18.24 (d,
J
CP
= 28.9 Hz, SiCH
2
).
31
P
{
1
H}
NMR (161.97 MHz,
THF
-
d
8
):
δ
13.5 (d,
J
= 11.7 Hz),
-
7
.5 (d,
J
= 11.7 Hz).
Anal. Calcd
(%) for
C
9
0
H
88
BF
24
NNiO
11
P
2
Si: C,
54.73
; H,
4.
49
; N,
0.
71
. Found(%): C,
5
3.95
; H,
4.
54
; N,
0.
98
.
(
2e
)
In a N
2
-
filled glovebox,
a dark orange solution of [(py)
2
Ni(CH
2
SiMe
3
)
2
] (31.5 mg, 0.080 mmol, 1 equiv.)
in benzene (3 mL) was added
t
o a colorless suspension of
1e
(139 mg, 0.080 mmol) in benzene (5 mL) in a
20 mL
scintillation
vial at room temperature. The resulting solution was stirred for 30 minutes, leading to
a light orange solution. All the volatiles were removed under reduced pressure and the residue was washed
with
n
-
pentane (2
× 5 mL). The resulting orange residue was extracted with benzene (15 mL) at room
temperature. The orange extract was evaporated under vacuum to obtain the product as an orange powder.
Yield: 131 mg (0.067 mmol, 83%).
1
H NMR (400.1 MHz, THF
-
d
8
):
δ 8.90 (m, 2H, py), 7.80 (br s, 8H, B(C
6
H
3
-
3,5
-
(CF
3
)
2
)
4
), 7.77 (m, 1H, py,
this signal partially overlaps with the signal at 7.80 ppm), 7.74 (dq,
J
= 11.2, 1.3 Hz,
1H, ArH), 7.58 (br s,
4H, B(C
6
H
3
-
3,5
-
(CF
3
)
2
)
4
), 7.52 (t,
J
= 8.4 Hz,
2H, ArH), 7.35 (t,
J
= 8.4 Hz,
2H, ArH), 7.20 (t,
J
= 6.8 Hz,
2H, py), 6.78 (dd, 3H, ArH+benzyl
-
H, two signals overlap with each other), 6.71 (dd,
J
= 10.4, 2.4 Hz,
2H,
benzyl
-
H), 6.65 (m,8H, ArH, two signals overlap with each other), 4.47 (d,
J
= 18.
2 Hz,
2H, CH
2
Ar), 3.56
(s, 12H, OCH
3
), 3.47 (s, 12H, OCH
3
), 2.12 (d,
J
= 1.9 Hz, Ar
-
Me
), 1.01 (s, 9H, C(CH
3
)
3
),
-
0.58 (s, 9H,
SiMe
3
),
-
0.83 (d,
J
= 9.3 Hz,
2H, NiCH
2
).
13
C
{
1
H}
NMR (101 MHz, THF
-
d
8
):
δ 173.76 (dd,
J
CP
= 25.0, 6.3
S
16
Hz, Ar
-
C)), 163.65 (s, Ar
-
C), 162.80 (q,
J
CF
= 50.0 Hz, Ar
F
-
C), 162.20 (d,
J
CP
= 1.6 Hz, Ar
-
C), 151.93 (s,
py), 138.06 (s, py), 136.57 (d,
J
CP
= 3.6 Hz, Ar
-
C), 136.05 (s, Ar
-
C), 135.58 (s, Ar
F
-
C), 134.79 (dd,
J
CP
=
12.8, 6.8 Hz, Ar
-
C), 133.87 (t,
J
CP
= 2.6 Hz, Ar
-
C), 132.75 (dd,
J
CP
= 9.2, 1.3 Hz, Ar
-
C), 131.92 (s, Ar
-
C),
131.37 (d,
J
CP
= 8.0 Hz, Ar
-
C), 130.47 (d,
J
CP
= 7.6 Hz, Ar
-
C), 130.0 (qq,
J
CF
= 31.5, 3.0 Hz, Ar
F
-
C), 129.18
(d,
J
CP
= 2.6 Hz, Ar
-
C), 129.13 (dd,
J
CP
= 51.4, 8.8 Hz, Ar
-
C), 125.49 (q,
J
CF
= 272.5 Hz, CF
3
), 125.04 (d,
J
CP
= 1.5 Hz, Ar
-
C), 118.16 (sept,
J
CF
= 4.0 Hz, Ar
F
-
C), 110.05 (d,
J
CP
= 50.5 Hz, Ar
-
C), 105.47 (d,
J
CP
=
4.3 Hz, Ar
-
C), 105.29 (d,
J
CP
= 6.3 Hz, Ar
-
C), 104.25 (d,
J
CP
= 11.0 Hz, Ar
-
C), 101.12 (d,
J
CP
= 90.5 Hz,
Ar
-
C), 55.97 (s, OCH
3
), 55.93 (s, OCH
3
),
34.31 (s,
C
(CH
3
)
3
), 33.03 (d,
J
CP
= 53.0 Hz, P
-
CH
2
), 31.89 (s,
C(
C
H
3
)
3
), 20.87 (d,
J
CP
= 1.1 Hz, Ar
-
C
H
3
), 1.95 (s, Si(CH
3
)
3
),
-
16.54 (d,
J
CP
= 30.3 Hz, SiCH
2
).
31
P
{
1
H}
NMR (161.97 MHz,
THF
-
d
8
): 14.3 (d,
J
= 12.8 Hz
),
-
6.4 (d,
J
= 12.8 Hz
).
Anal.
Calcd
(%) for
C
90
H
8
2
BF
24
NNiO
9
P
2
Si: C,
56.02
; H,
4.
34
; N,
0
.72
. Found(%): C,
55.54;
H,
4.3
2
; N,
0.5
6
.
(
2f
)
In a N
2
-
filled glovebox,
a dark orange solution of [(py)
2
Ni(CH
2
SiMe
3
)
2
] (22 mg, 0.056 mmol, 1 equiv.) in
benzene (3 mL) was added
t
o acolorless suspension of
1f
(100 mg, 0.056 mmol) in benzene (5 mL) in a 20
mL
scintillation
vial at room temperature. The resulting solution was stirred for 30 minutes, leading to a
light orange solution. All the volatiles were removed under reduced pressure and the residue was washed
with
n
-
pentane (2
× 5 mL). The resulting oily residue was extracted with benzene (10 mL) at room
temperature. The orange extract was evaporated under vacuum to obtain the product as an orange powder.
Yield: 107 mg (0.053 mmol, 95%).
1
H NMR (400.1 MHz, C
6
D
6
):
δ 8.55 (m, 2H, py), 8.43 (br s, 8H, B(C
6
H
3
-
3,5
-
(CF
3
)
2
)
4
), 7.70 (dq,
J
= 11.2,
1.2 Hz,
1H, ArH; this signal partially overlaps with the signal at 7.67ppm), 7.67 (br s, 4H, B(C
6
H
3
-
3,5
-
(CF
3
)
2
)
4
), 7.12 (t,
J
= 8.4 Hz,
2H, ArH), 7.00 (t,
J
= 8.4 Hz,
2H, ArH), 6.94 (m, 3H, ArH + py), 6.74 (d,
J
=
S
17
7.8 Hz,
2H, ArH), 6.58 (dd,
J
= 17.7, 2.4 Hz,
1H, ArH), 6.40 (t,
J
= 6.9 Hz,
2H, py), 6.25 (dd,
J
= 8.4, 3.7 Hz,
4H, ArH), 6.02 (dd,
J
= 8.5, 5.0 Hz,
4H, ArH), 4.33 (d,
J
= 18.7 Hz,
2H, CH
2
Ar), 3.16 (s, 12H, OCH
3
), 2.99
(s, 12H, OCH
3
),
0.94 (s, 9H, C(CH
3
)
3
),
-
0.22 (s, 9H, SiMe
3
),
-
0.62 (d,
J
= 9.1 Hz,
2H, NiCH
2
).
13
C
{
1
H}
NMR
(101 MHz, THF
-
d
8
):
δ 173.67 (dd,
J
CP
= 25.0, 5.9 Hz, Ar
-
C)), 163.74 (s, Ar
-
C), 162.80 (q,
J
CF
= 50.0 Hz,
Ar
F
-
C), 162.13 (d,
J
CP
= 1.5 Hz, Ar
-
C), 151.84 (s, py), 139.26 (dd,
J
CP
= 7.7, 1.5 Hz, Ar
-
C), 138.14 (s, py),
136.53 (s, Ar
-
C), 135.57 (s, Ar
F
-
C), 135.22 (dd,
J
CP
= 12.8, 6.2 Hz, Ar
-
C), 134.27 (t,
J
CP
= 2.6 Hz, Ar
-
C),
132.19 (dd, Ar
-
C; this signal overlaps with the signal at 132.12 ppm), 132.12 (s, Ar
-
C), 131.03 (d,
J
CP
= 7.5
Hz, Ar
-
C),130.0 (qq,
J
CF
= 31.5, 3.0 Hz, Ar
F
-
C), 129.38 (d,
J
CP
= 8.8 Hz, Ar
-
C), 128.87 (d,
J
CP
= 8.8 Hz, Ar
-
C), 125.49 (q,
J
CF
= 272.5 Hz, CF
3
), 125.22 (m, Ar
-
C), 125.18 (q,
J
CF
= 272.0 Hz, CF
3
), 125.06 (d,
J
CP
= 1.5
H
z, Ar
-
C), 118.17 (sept,
J
CF
= 4.0 Hz, Ar
F
-
C), 109.64 (d,
J
CP
= 50.7 Hz, Ar
-
C), 105.46 (d,
J
CP
= 6.2 Hz, Ar
-
C), 104.85 (d,
J
CP
= 10.8 Hz, Ar
-
C), 103.88 (d,
J
CP
= 11.0 Hz, Ar
-
C), 100.50 (d,
J
CP
= 92.1 Hz, Ar
-
C), 56.10
(s, OCH
3
), 55.89 (s, OCH
3
), 34.31 (s,
C
(CH
3
)
3
), 32.71 (d,
J
CP
= 54.5 Hz, P
-
CH
2
), 31.82 (s, C(
C
H
3
)
3
), 1.96 (s,
Si(CH
3
)
3
),
-
16.27 (d,
J
CP
= 30.1 Hz, SiCH
2
).
31
P
{
1
H}
NMR (161.97 MHz, C
6
D
6
):
δ
13.4 (dq,
J
= 12.8, 2.0
Hz
),
-
6.5 (d,
J
= 12.8 Hz
).
19
F NMR (376.16 MHz, C
6
D
6
):
δ
62.21 (s, 24F),
-
62.44 (s, 3F).
Anal. Calcd
(%)
for C
9
1
H
81
BF
27
NNiO
9
P
2
Si: C,
5
4.
51
; H,
4
.0
7
; N,
0.
70
. Found(%): C,
5
3.31
;
H,
3.71
; N,
0.5
9.
(
2g
)
In a N
2
-
filled glovebox,
a dark orange solution of [(py)
2
Ni(CH
2
SiMe
3
)
2
] (22.9 mg, 0.059 mmol, 1 equiv.)
in benzene (3 mL) was added
t
o acolorless suspension of
2g
(107 mg, 0.059 mmol) in benzene (5 mL) in a
20 mL
scintillation
vial at room temperature. The resulting solution was stirred for 20 minutes, leading to
a light orange solution. All the volatiles were removed under reduced pressure and the residue was washed
with
n
-
pentane (2
× 3 mL). The resulting oily residue was extracted with benzene (15 mL) at room
S
18
temperature. The filtrate was dried under vaccum to obtain the product as an orange powder Yield: 97 mg
(0.047 mmol, 80%).
1
H NMR (400.1 MHz, C
6
D
6
):
δ 8.67 (m, 2H, py), 8.44 (br s, 8H, B(C
6
H
3
-
3,5
-
(CF
3
)
2
)
4
), 7.77 (dq,
J
= 11.2,
1.2 Hz, 1H, ArH), 7.69 (br s, 4H, B(C
6
H
3
-
3,5
-
(CF
3
)
2
)
4
), 7.06 (t,
J
= 8.3 Hz, 2H, ArH), 6.98 (t,
J
= 8.3 Hz,
2H, ArH), 6.96
–
6.80 (m, 3H, ArH + py), 6.61 (s, 2H, ArH), 6.47 (t,
J
= 6.8 Hz, 2H, py), 6.23(dd,
J
= 8.3,
3.7 Hz, 4H, ArH), 6.01 (dd,
J
= 8.5, 4.8 Hz,4H, ArH), 4.47 (d,
J
= 17.7 Hz, 2H, CH
2
Ar), 3.16 (s, 12H,
OCH
3
), 2.91 (s, 12H, OCH
3
), 1.08 (s, 9H, C(CH
3
)
3
), 1.05 (s, 18H, C(CH
3
)
3
),
-
0.26 (s, 9H, SiMe
3
),
-
0.63 (d,
J
= 9.2 Hz, 2H, NiCH
2
).
13
C
{
1
H}
NMR (101 MHz, THF
-
d
8
):
δ 173.85 (dd,
J
CP
= 25.0, 6.2 Hz, Ar
-
C)),
163.70 (s, Ar
-
C), 162.80 (q,
J
CF
= 50.0 Hz, Ar
F
-
C), 162.17 (d,
J
CP
= 1.5 Hz, Ar
-
C), 151.93 (s, py), 150.93
(s,Ar
-
C), 138.10 (s, py), 136.09 (s, Ar
-
C), 135.58 (s, Ar
F
-
C), 135.10 (s, Ar
-
C), 134.93 (dd,
J
CP
= 12.8, 6.2 Hz,
Ar
-
C), 134.42 (d,
J
CP
= 7.4 Hz, Ar
-
C),134.02 (t,
J
CP
= 2.6 Hz, Ar
-
C), 132.19 (dd,
J
CP
= 9.8, 1.5 Hz, Ar
-
C),
131.91 (s, Ar
-
C), 130.01 (qq,
J
CF
= 31.5, 3.0 Hz, Ar
F
-
C), 129.74 (d,
J
CP
= 8.8 Hz, Ar
-
C), 129.24 (d,
J
CP
= 8.8
Hz, Ar
-
C), 129.01 (s, Ar
-
C), 125.49 (q,
J
CF
= 272.0 Hz, CF
3
), 124.88 (d,
J
CP
= 1.3 Hz, Ar
-
C), 124.15 (d,
J
CP
= 8.8 Hz, Ar
-
C), 120.76 (d,
J
CP
= 2.0 Hz, Ar
-
C), 118.16 (sept,
J
CF
= 4.0 Hz, Ar
F
-
C), 110.11 (d,
J
CP
= 50.6
Hz, Ar
-
C), 106.09 (d,
J
CP
= 10.8 Hz, Ar
-
C), 105.42 (m,Ar
-
C), 105.14 (d,
J
CP
= 11.0 Hz, Ar
-
C), 100.86 (d,
J
CP
= 92.2 Hz, Ar
-
C), 56.05 (s, OCH
3
), 55.89 (s, OCH
3
), 35.20 (s,
C
(CH
3
)
3
), 34.45 (s,
C
(CH
3
)
3
), 33.94 (d,
J
CP
= 56.2 Hz, P
-
CH
2
), 32.01 (s, C(
C
H
3
)
3
), 31.66 (s, C(
C
H
3
)
3
), 1.84 (s, Si(CH
3
)
3
),
-
16.59 (d,
J
CP
= 30.1 Hz,
SiCH
2
).
31
P
{
1
H}
NMR (161.97 MHz, C
6
D
6
): δ 11.6 (d,
J
= 12.2 Hz),
-
6.7 (d,
J
= 12.2 Hz).
Anal. Calcd
(%)
for C
9
8
H
98
BF
24
NNiO
9
P
2
Si: C,
57.
44
; H,
4.
82
; N,
0.
68
. Found(%): C,
57.08
; H,
4.48
; N,
0.
24
.
(
2
a'
)
In a N
2
-
filled glovebox,
1
a'
(66 mg, 0.07 mmol) and
[
(py)
2
Ni(CH
2
SiMe
3
)
2
]
(28 mg, 0.07 mmol, 1 equiv.)
were dissolved in 5 mL of benzene
i
n a 20 mL scintillation vial,
forming a dark red solution. The mixture
was stirred for 20 minutes at room temperature and the solvent was removed in
vacuo
to yield a dark brown
S
19
sticky gel. Trituration with
n
-
pentane afforded a brown solid, which was washed with 3 x 3 mL of cold
diethyl ether. All the volatiles were removed in
vacuo
, providing
2
a'
as a brown powder.The ether washings
were combined and
stored at room temperature for a week to afford dark red crystals of
2
a'
. Yield: 66 mg
(0.06mmol, 80%).
1
H NMR (400 MHz, THF
-
d
8
): δ 8.72
–
8.65 (m, 2H, ArH), 7.86 (tt,
3
J
HH
= 7.6, 1.7 Hz, 1H, ArH), 7.76
(ddd,
4
J
HP
= 11.1 Hz,
4
J
HH
= 2.5 Hz,
5
J
HP
= 1.2 Hz, 1H, ArH), 7.57 (t,
3
J
HH
= 8.4 Hz, 2H, PArH), 7.33 (t,
3
J
HH
= 8.3 Hz, 2H, PArH), 7.17 (t, J = 6.7 Hz, 2H, Py), 6.79 (dd,
3
J
HH
= 8.4,
4
J
HH
= 4.9 Hz, 4H, PArH),
6.67 (d, J = 3.7 Hz, 2H), 6.65 (d, J = 3.8 Hz, 2H),6.60 (dd,
4
J
HH
= 2.5 Hz,
5
J
HP
= 0.9 Hz, 1H, ArH), 3.67 (s,
12H, OCH
3
), 3.63 (s, 12H, OCH
3
), 2.39 (d,
2
J
HP
= 15.6 Hz, 3H, PCH
3
), 1.01 (s, 9H, C(CH
3
)
3
),
-
0.59 (s, 9H,
Si(CH
3
)
3
),
-
0.87 (d,
3
J
HP
= 9.4 Hz, 2H, SiCH
2
).
13
C{
1
H} NMR (101 MHz, THF
-
d
8
): δ 174.03
(dd,
J
CP
= 24.7,
5.7 Hz, Ar
-
C)),
163.89 (s,Ar
-
C), 162.12 (d,
J
CP
= 1.5 Hz,
Ar
-
C), 151.38 (s, Ar
-
C), 138.87 (s,Ar
-
C), 136.55
(s,Ar
-
C), 134.89 (dd,
J
CP
= 13.0, 5.9 Hz,
Ar
-
C),
133.84 (t,
J
CP
= 2.8 Hz,
Ar
-
C), 131.79 (s,Ar
-
C), 130.67 (d, J
CP
= 11.3 Hz,Ar
-
C), 128.40 (dd,
J
CP
= 50.6, 8.2 Hz, Ar
-
C)),
125.16 (s, Ar
-
C), 110.13
(d,
J
CP
= 49.5 Hz, Ar
-
C),107.56 (dd,
J
CP
= 99.7, 10.6 Hz, Ar
-
C),
105.99 (d, J = 6.4 Hz,Ar
-
C), 105.25 (d, J = 4.3 Hz, Ar
-
C), 100.93
(d, J = 95.7 Hz, Ar
-
C), 56.80 (s, O
C
H
3
), 55.98 (s, O
C
H
3
) , 34.38 (s, C(CH
3
)
3
), 31.99 (s, C(CH
3
)
3
), 14.30 (d,
2
J
CP
= 64.3 Hz, PCH
3
),1.96 (s, Si(CH
3
)
3
),
-
16.95 (d,
2
J
CP
= 29.3 Hz, SiCH
2
).
19
F{
1
H} NMR (362 MHz, THF
-
d
8
): δ
-
78.33 (s, CF
3
).
31
P{
1
H} NMR (162 MHz, THF
-
d
8
):
δ
7.62 (d,
4
J
PP
= 12.3 Hz, PAr
2
Me
+
),
-
7.19 (d,
4
J
PP
= 11.9 Hz, PAr
2
).
Anal. Calcd
(%) for C
53
H
66
F
3
NNiO
9
P
2
S
Si: C,
55.
51
; H,
5.8
; N,
1.22
. Found
(%): C,
54.72
;
H,
5.68
; N,
1.11
.
S
20
4.
NMR spectra
Figure S1
.
1
H NMR spectrum of
2a
in THF
-
d
8
.
Figure S2
.
31
P
{
1
H}
NMR spectrum of
2a
in THF
-
d
8
.