Organometallics
Article
1
MHz, CD Cl ): δ −127.68 (t, J = 12 Hz, 2F, F14), −128.97 (m, 1F,
H4), 1.51 (br. s, 2H, H4). 13C{ H} NMR (101 MHz, CD Cl ): δ
2
2
FF
2 2
F12), −133.18 (br. s, ν = 40 Hz, 16F, o-C F ), −153.24 (t, J = 18
213.39 (C16), 164.41 (C10), 160.09 (C5), 153.10 (C9), 145.37
(C15), 140.51 (C7), 136.10 (C12), 135.30 (C17), 135.26 (C14),
134.34 (C20), 133.53 (C11), 130.11 (C18), 129.38 (C19), 125.67
(C8), 125.57 (C13), 123.44 (C6), 68.30 (C2), 46.81 (C3), 23.87
1
/2
6
5
FF
Hz, 4F, F13), −163.46 (t, J = 20 Hz, 8F, p-C F ), −167.48 (t, J
=
FF
6
5
FF
1
7 Hz, 16F, m-C F ). The majority of peaks visible in the NMR
6 5
spectra that are not from 5 are from 4. Anal. Calcd for
1
9
C H B F N OPd: C, 45.38; H, 1.47; N, 2.82. Found: C, 45.39;
(C4), 11.56 (C1). F NMR (376 MHz, CD Cl ): δ −133.08 (br. s,
75
29
2
45
4
2
2
3
H, 1.72; N, 2.88.
ν1/2 = 40 Hz, 8F, o-C F ), −163.72 (t, J = 20 Hz, 4F, p-C F ),
6
5
FF
6 5
3
−
167.57 (t, J = 18 Hz, 8F, m-C F ). Before EA, 7 was placed under
FF 6 5
high vacuum for 72 h and afterward was found to contain 0.3 equiv of
dichloromethane by H NMR. Anal. Calcd for C H BF N OPd·0.3
CH Cl : C, 51.40; H, 2.31; N, 3.37. Found: C, 51.05; H, 2.26; N,
1
5
3
28
20
3
2
2
3.40.
[
(pyrHCPy )Pd(C H (OCC H ))] [BArF4−]2 (6). Compound 4
2+
2 6 4 6 5
(
161 mg, 0.077 mmol, 1.0 equiv) was added to a 20 mL scintillation
vial with a stir bar and 10 mL of dichloromethane. Benzophenone
139 mg, 0.77 mmol, 10 equiv) was added, and the solution was
(
allowed to stir for 6 h. The light purple color of the solution gradually
changes to red and eventually to a pale yellow. The solvent was
removed in vacuo. Then, 2 mL of diethyl ether was added to the
residue, and 10 mL of hexane was added to crash out a pale yellow
powder. The powder was washed twice with hexane and then put
under reduced pressure to dry. The same procedure can be repeated
+
F −
[
(pyrCPy )Pd(C H (NC H ))] [BAr ] (8). Compound 2 (136 mg,
2 6 4 5 4 4
0
.285 mmol, 1.0 equiv) was added to a 25 mL Schlenk flask with 10
mL of dichloromethane and 2-phenylpyridine (44 μL, 0.285 mmol,
+
F
−
1
.0 equiv). [H(OEt ) ] [BAr ] (255 mg, 0.285 mmol, 1.0 equiv)
2 2 4
was slowly added over a minute to the solution with vigorous stirring.
After 48 h of stirring, the reaction mixture showed a mixture of
products by H NMR. 2-Phenylpyridine (44 μL, 0.285 mmol, 1.0
equiv) and potassium carbonate (200 mg, 1.45 mmol, 5.1 equiv) was
added to the reaction mixture and left to stir for another 48 h. The
solids were removed by filtration, and the yellow filtrate was layered
with an equivalent volume of hexane in a 20 mL scintillation flask for
recrystallization. Large yellow crystals were visible (261 mg, 71%). H
NMR (400 MHz, CD Cl ): δ 8.90 (br. s, 2H, H9), 8.03−7.95
multiple peaks, 4H, H20, H18, and H7), 7.90 (d, J = 8 Hz, 1H,
H17), 7.71 (d, JHH = 8 Hz, 2H, H6), 7.62 (d, JHH = 8 Hz, 1H, H14),
7.50 (t, JHH = 6 Hz, 2H, H8), 7.23 (multiple peak, 2H, H13 and
H12), 7.13 (t, JHH = 8 Hz, 1H, H19), 6.76 (d, JHH = 8 Hz, 1H, H11),
.56 (br. s, 4H, H3), 2.15 (s, 3H, H1), 1.56 (m, 2H, H4), 1.31 (m,
H, H4 (overlaid with hexane)). C{ H} NMR (101 MHz, CD Cl ):
δ 166.27 (C16), 161.04 (C5), 155.76 (C10), 148.67 (C20), 145.54
C15), 140.45 (C7), 139.86 (C18), 133.44 (C11), 130.53 (C12),
25.70 (C8), 125.53 (C13), 124.31 (C14), 123.38 (C19), 123.22
1
with 5 to achieve the same results. Yield: 130 mg, 90%. H NMR (400
1
MHz, CD Cl ): δ 11.90 (br. s, 1H, H7), 9.20 (d, J = 6 Hz, 1H,
2
2
HH
H17), 9.14 (d, JHH = 5 Hz, 1H, H12), 8.37 (t, JHH = 8 Hz, 1H, H15),
.30 (t, JHH = 8 Hz, 1H, H10), 8.02 (overlaid doublets, 2H, H9 and
8
H14), 7.96 (d, JHH = 8 Hz, 2H, H26), 7.91−7.86 (multiple peaks, 4H,
H16, H11, H28, and H22), 7.68 (t, JHH = 8 Hz, 2H, H27), 7.56 (t,
JHH = 8 Hz, 1H, H20), 7.49 (t (second-order coupling), 1H, H21),
1
6
3
.91 (d, JHH = 8 Hz, 1H, H19), 3.52−3.34 (m, 2H, H3 or H6), 3.34−
2
2
(
.19 (m, 2H, H3 or H6), 2.49 (s, 3H, H1), 2.32−2.06 (m, 4H, H4
HH
1
and H5). Free benzophenone is observed at 7.78 in the H NMR
spectrum. 1 C{ H} NMR (101 MHz, CD Cl ): δ 216.59 (C24),
3
1
2
2
1
62.18 (C18), 157.52 (C17), 152.95 (C12), 151.40 (C13), 149.31
2
2
(
(
(
(
1
(
C8), 148.52 (d, JCF = 241 Hz, o-B(C F ) ), 147.02 (C23), 144.05
C15), 143.62 (C10), 138.58 (d, JCF = 245 Hz, p-B(C F ) ), 138.46
C20), 137.88 (C22), 136.71 (d, JCF = 248 Hz, m-B(C F ) ), 136.67
C28), 133.56 (C21), 133.51 (C25), 133.11 (C19), 131.04 (C26),
30.36 (C16), 129.92 (C27), 129.08 (C11), 126.66 (C14), 126.05
C9), 72.17 (C2), 52.54 (C3 or C6), 52.47 (C3 or C6), 25.20 (C4 or
6
5 4
1
3
1
2
2
6
5 4
6
5 4
(
1
(
1
9
C6), 68.53 (C2), 46.84 (C3), 23.80 (C4), 11.28 (C1). F NMR
1
9
(376 MHz, CD Cl ): δ −133.06 (br. s, ν = 40 Hz, 8F, o-C F ),
C5), 25.08 (C4 or C5), 15.20 (C1). F NMR (376 MHz, CD Cl ): δ
2
2
1/2
6 5
2
2
3
3
3
−163.70 (t, J = 20 Hz, 4F, p-C F ), −167.56 (t, J = 18 Hz, 8F,
−
133.99 (br. s, ν1/2 = 40 Hz, 16F, o-C F ), −163.29 (t, J = 20 Hz,
F, p-C F ), −167.32 (t, J = 18 Hz, 16F, m-C F ). Compound 6
FF
6
5
FF
6
5
FF
3
m-C F ). Before EA, 8 was placed under high vacuum for 72 h and
8
6 5
6
5
FF
6 5
1
afterward was found to contain 0.2 equiv of dichloromethane by H
NMR. Anal. Calcd for C H BF N Pd·0.2 CH Cl : C, 50.82; H,
was not found to be analytically pure by EA. Deprotonation of 6
followed by recrystallization removes the impurity.
51 27
20
4
2
2
2
.28; N, 4.63. Found: C, 51.02; H, 2.66; N, 4.41.
[
(pyrCPy )Pd(C H (OCC H ))] [BAr ] (7). Compound 6 (100
+
F −
2 6 4 6 5 4
[(pyrHCPy )Pd(C H (OCC H ))] [SbF ] (10). Compound 3 (46
2+
−
mg, 0.082 mmol, 1.0 equiv) was added to a 20 mL scintillation vial
with 5 mL of dichloromethane. Potassium carbonate (73 mg, 0.53
mmol, 10 equiv) was added and the mixture was left to stir for 18 h.
The solids are removed from the red solution by filtration, and the
filtrate was placed under reduced pressure to yield a red powder. 7 can
be recrystallized from dichloromethane (∼5 mL/100 mg) layered
with an equal amount of hexane to give large red crystals after a few
days (42 mg, 65%). The leftover solvent can be reduced and relayered
with hexane to produce more crystals although the yield will be
2
6
4
6
5
6
2
mg, 0.107 mmol, 1.0 equiv), benzophenone (195 mg, 1.07 mmol, 10
equiv) and 10 mL of dichloromethane to a 25 mL Schlenk flask.
AgSbF (73.4 mg, 0.214 mmol, 2.0 equiv) was added to the stirred
solution and AgCl quickly precipitated. The reaction was left to stir
overnight. The AgCl was removed by filtration. The solvent was
removed under reduced pressure, and the residue was washed twice
with hexane to remove excess benzophenone. The residue was
dissolved in ∼5 mL of dichloromethane and layered with an equal
amount of hexane and left at room temperature overnight. Crystals
6
1
significantly less than the first. H NMR (400 MHz, CD Cl ): δ 9.01
2
2
1
(
(
d, JHH = 5 Hz, 2H, H9), 8.00 (t, JHH = 8 Hz, 2H, H7), 7.90 (d
second-order coupling), 2H, H17), 7.78−7.71 (multiple peaks, 3H,
suitable for X-ray diffraction were available the next day. The H
F
4
−
NMR spectrum was consistent with that of the [BAr ] analog.
pyrH
2+
−
H19 and H6), 7.69 (d, J = 8 Hz, 1H, H13), 7.62 (t (second-order
[( CPy )Pd(C H (NC H ))] [SbF ] (11). Compound 3 (49
HH
2 6 4 5 4 6 2
coupling), 2H, H18), 7.50 (ddd, JHH = 5 Hz, 2H, H8), 7.42 (t, JHH
=
mg, 0.114 mmol, 1.0 equiv) was added to a 25 mL Schlenk flask with
7
Hz, 1H, H11), 7.28 (t, JHH = 8 Hz, 1H, H12), 6.94 (d, JHH = 8 Hz,
H, H10), 2.47 (br. s, 4H, H3), 2.11 (s, 3H, H1), 1.64 (br. s, 2H,
12 mL of dichloromethane and was stirred vigorously. AgSbF (39
6
1
mg, 0.114 mmol, 1.0 equiv) was added to the solution to generate a
F
Organometallics XXXX, XXX, XXX−XXX