Organometallics
Article
1
3JPC = 10.6, m-Ph), 125.3 (m-py), 60.1 (−OCH CH ), 16.1 (d, J
3
NMR (CD Cl ): δ 18.4 (s, PO), −29.1 (s, P). H NMR (CD Cl ):
=
PC
2
2
2
2
2
3
D
H
B
C
E
δ 12.12 (s, 1H, −OH), 8.06 (m, 1H, H ), 7.36 (m, 4H, H , H , H ),
.09 (m, 1H, H ), 6.91 (m, 2H, H ), 6.87 (t, 2H, H ), 6.68 (t, 2H, H ),
8, −OCH CH ), 0.7 (Pd−CH ), C not observed. HRMS: calcd. for
2
3
3
A
G
I
J
+
7
4
6
1
(
1
1
[C H P O NPd] , m/z 570.0579. Found: 570.0563.
26 28 2 3
3
2
i
.60 (m, 1H, −OCH(CH ) ), 3.66 (s, 6H, −OCH ), 1.01 (d, J = 6,
(κ -P,O-1-PPh -2-PO Pr-Ph)PdMe(2,6-lutidine) (2c-lut). 2c-lut
2 3
was synthesized using a similar procedure to 2a-lut with (TMEDA)-
PdMe (0.079 g, 0.313 mmol), H[1c] (0.120 g, 0.313 mmol), 2,6-
lutidine (0.04 mL, 0.313 mmol), and CH Cl (10 mL). 2c-lut was
3
2
3
HH
1
3
1
2
H, −OCH(CH ) ). C{ H} NMR (CD Cl ): δ 161.4 (d, J
=
3
2
2
2
PC
K
F
1
2
E
4.3, C ), 138.5 (br, C ), 137.0 (dd, J = 191, J = 32.1, C ), 135.8
PC
PC
2
2
A
J
2
3
D
d, J = 15.1, C ), 134.3 (s, C ), 134.0 (dd, J = J = 10, C ),
PC
PC
PC
2
2
B
H
3
C
L
31
1
31.8 (C ), 131.2 (C ), 129.3 (d, J = 13.7, C ), 123.3 (br, C ),
obtained as a white solid (0.068 g, 36%). P{ H} NMR (CD Cl ): δ
2 2
PC
I
G
2
28.7 (d, 3JPP = 16, PO), 7.8 (d, JPP = 17, P−Pd). H NMR
3
1
21.4 (C ), 110.9 (C ), 71.1 (d, J = 6.3, −OCH(CH ) ), 56.0
PC
3 2
3
D
(
−OCH ), 23.8 (d, J = 4.5, −OCH(CH ) ). ESI-MS (CH Cl /
3
PC
3
2
2
2
(CD Cl ): δ 8.17 (m, 1H, H ), 7.65 (m, 4H, o-Ph), 7.55 (br t, 1H, p-
2
2
C
3
MeOH 1:1 volume, pos. scan, m/z): 445.2. HRMS: calcd. for
lut), 7.47 (m, 6H, m-Ph, p-Ph), 7.42 (m, 1H, H ), 7.33 (t, J = 7.5,
1H, H ), 7.20 (d, J = 8, 2H, m-lut), 7.08 (m, 1H, H ), 4.21 (m, 1H,
HH
+
B
3
A
[
C H O P ] , m/z 445.1334. Found: 445.1338.
(
23 27 5 2
HH
2
3
κ -P,O-1-PPh -2-PO Ph-Ph)PdMe(2,6-lutidine) (2a-lut). A vial
2 2
−OCH(CH ) ), 3.16 (s, 6H, lut−CH ), 0.56 (d, J = 5.5, 6H,
3
2
3
HH
13
was charged with H[1a] (0.191 g, 0.476 mmol) and (TMEDA)PdMe2
0.124 g, 0.491 mmol), and a solution of 2,6-lutidine (0.105 g, 0.980
mmol) in CH Cl (8 mL) was added. The resulting clear solution was
stirred for 7 h at room temperature. The volatiles were removed under
vacuum to afford a white solid. The solid was suspended in Et O,
collected by filtration, and dried under vacuum. The crude solid was
found to contain 0.59 equiv of CH Cl and 0.07 equiv of Et O (0.300
g, 92%). X-ray quality crystals of 2a-lut·CH Cl were grown from a
CH Cl /THF solution that was cooled to −40 °C for ca. 10 weeks. As
described in the text, dissolution of this compound in CD Cl
generated a mixture of 2a-lut, free 2,6-lutidine, and a species
formulated as the base-free species {(κ -1-PPh -2-PO Ph-Ph)PdMe} ,
which partially precipitates from solution. Addition of excess 2,6-
3
1
−OCH(CH ) ), −0.05 (d, J = 2.5, 3H, Pd−CH ). C{ H} NMR
3
2
PH
3
(
1
2
E
(
CD Cl ): δ 158.9 (o-lut), 144.8 (dd, J = 165, J = 19, C ), 138.6
2 2 PC PC
D
2
2
2
(p-py), C obscured by o-Ph, 134.7 (d, J = 12, o-Ph), 134.4 (dd, J
PC PC
A
1
2
F
1
=
11, 7.8, C ), 133.5 (dd, J = 45.7, J = 6.5, C ), 131.4 (d, J
PC
=
PC
PC
4
2
53.2, ipso-Ph), 130.8 (d, J = 2.4, p-Ph), 130.4 (dd, J = 12, 2.4,
C ), 129.3 (dd, J = 7, 2.4, C ), 128.8 (d, J = 10.9, m-Ph), 122.8,
(m-lut), 68.6 (d, J = 5.8, −OCH(CH ) ), 26.5 (lut−CH ), 23.5 (d,
JPC = 4, −OCH(CH ) ), −5.2 (d, J = 4, Pd−CH ). HRMS calc. for
PC PC
C
B
3
PC
PC
2
2
2
2
PC
3
2
3
3
2
2
2
3
2
PC
3
+
2
2
[
C H NO P Pd] m/z 612.10488. Found: 612.1036.
29 34 3 2
2
i
2
2
(
κ -P,O-1-PPh -2-PO Pr-Ph)PdMe(pyridine) (2c-py). 2c-py
2 3
was synthesized using a similar procedure to 2a-lut with (TMEDA)-
PdMe (0.139 g, 0.552 mmol), H[1c] (0.212 g, 0.552 mmol), pyridine
0.09 mL, 1.12 mmol), and CH Cl (10 mL). 2c-py was obtained as
2
2
2
n
2
(
2 2
lutidine converts the base-free compound back to 2a-lut. Data for 2a-
31
1
an off-white solid (0.128 g, 40%). P{ H} NMR (CD Cl ): δ 32.4 (d,
lut: 31P{ H} NMR (CD Cl ): δ 31.4 (d, J = 14, P−Pd), 17.4 (d, J
1
3
3
2
2
2
2
PP
PP
3
3
1
JPP = 14, PO), 8.6 (d, J = 14, P−Pd). H NMR (CD Cl ): δ 8.87
1
PP
2
2
=
14, PO). H NMR (CD Cl ), most aryl signals are multiplets that
2
2
3
D
3
(
d, J = 4, 2H, o-py), 8.20 (m, 1H, H ), 7.87 (br t, J = 7.5, 1H, p-
HH HH
overlap with signals for free 2,6-lutidine and the base-free species; the
3
C
py), 7.60 (m, J = 7, 4H, o-Ph), 7.5−7.42 (m, 9H, H , m-py, m-Ph,
p-Ph), 7.31 (t, J = 7.5, 1H, H ), 7.05 (m, 1H, H ), 4.23 (m, 1H,
HH
following signals were resolved and identified as belonging to 2a-lut: δ
.87 (dddd, J = 11.9, 7.7, 3.8, 0.9, 1H), 7.63 (t, J = 7.6, 1H), 3.18 (s,
H), −0.03 (d, J = 3.2, 3H, Pd−CH ). Data for {(κ -1-PPh -2-
PO Ph-Ph)PdMe} : P{ H} NMR (CD Cl ): δ 30.6 (br), δ 16.8 (br).
3
B
A
HH
7
6
3
3
3
2
−OCH(CH
3
)
2
) 0.70 (d, JHH = 6.0, 6H, −OCH(CH
3
)
2
), 0.25 (d, JPH
PH
3
2
13
1
31
1
= 2, 3H, Pd−CH ). C{ H} NMR (CD Cl ): δ 150.5 (o-py), 144.1
3 2 2
(dd, JPC = 168, JPC = 19, C ), 138.4 (p-py), C obscured by o-Ph and
C , 134.7 (d, JPC = 12, o-Ph), 134.6 (dd, JPC = 3.1, 10.3, C ), 132.8 (d,
JPC = 44.1, C ), 131.3 (d, J = 53.3, ipso-Ph), 130.9 (d, J = 2.1, p-
Ph), 130.5 (dd, JPC = 11, 4, C ), 129.5 (dd, JPC = 7.2, 2.3, C ), 128.8
d, JPC = 10.9, m-Ph), 125.2, (m-py), 68.3 (d, JPC = 5.5,
OCH(CH ) ), 23.9 (d, J = 4, −OCH(CH ) ), 0.6 (Pd−CH ).
HRMS calc. for [C H NO P Pd] m/z 584.07358. Found: 584.0724.
(κ -P,O-1-PAn -2-PO Pr-Ph)PdMe(pyridine) (2d-py). 2d-py
was synthesized using a similar procedure to 2a-lut with (TMEDA)-
PdMe (0.118 g, 0.465 mmol), H[1d] (0.206 g, 0.464 mmol), pyridine
(80 μL, 0.99 mmol), and CH Cl (10 mL). 2d-py was obtained as an
off-white solid (0.161 g, 54%). P{ H} NMR (CD Cl ): δ 24.6 (br,
PO), 9.1 (d, J = 11.9, P−Pd). H NMR (CD Cl ): δ 8.89 (d, J
= 3.0, 2H, o-py), 8.10 (m, 1H, H ), 7.84 (t, J = 7.5, 1H, p-py), 7.52
HH
2
n
2
2
1
2
E
D
1
3
H NMR (CD Cl ): δ 8.23 (m), 0.235 (d, J
= 2.8, Pd−CH3).
2
2
PH
A
2
A
+
HRMS: calcd. for [C H O P NPd] m/z 630.09431. Found:
3
2
32
2
2
1
F
1
4
PC
PC
6
30.0919.
(
C
B
2
κ -P,O-1-PPh -2-PO Et-Ph)PdMe(2,6-lutidine) (2b-lut). 2b-lut
was synthesized using a similar procedure to 2a-lut with (TMEDA)-
PdMe (0.147 g, 0.581 mmol), H[1b] (0.215 g, 0.581 mmol), 2,6-
lutidine (0.12 mL, 1.0 mol), and CH Cl (10 mL). 2b-lut was obtained
as a white solid (0.174 g, 44%). P{ H} NMR (CD Cl ): 28.5 (d, J
2 3
3
2
(
−
3
3
2
PC
3
2
3
2
+
2
7
30
3 2
2
2
2
i
31
1
3
2 3
2
2
PP
3
1
=
1
7
16, PO), 9.4 (d, J = 17, P−Pd). H NMR (CD Cl ): 8.17 (m,
PP
2
2
D
3
2
H, H ), 7.65 (t, J = 7, 1H, p-lut), 7.60 (m, 4H, o-Ph), 7.47 (m,
HH
C
B
3
H, H , m-Ph, and p-Ph), 7.34 (m, 1H, H ), 7.18 (d, J = 8, 2H, m-
2
2
HH
31
1
A
lut), 7.03 (m, 1H, H ), 3.15 (br, 8H, −OCH CH and lut−CH ), 0.56
2 2
2
3
3
3
1
3
3
3
(
t, J = 7, 3H, −OCH CH ), 0.04 (d, J = 3.0, 3H, Pd−CH ).
PP
2
2
HH
HH
2
3
PH
3
D
3
1
3
1
1
2
C{ H} NMR (CD Cl ): δ 159.0 (o-lut), 143.2 (dd, J = 163, J
=
=
2
2
PC
PC
3
H
J
C
E
D
2
(t, J = 7.5, 2H, H ), 7.46−7.41 (m, 5H, m-py, H , H ), 7.23 (t,
3 B A I G
HH
1
1
9, C ), 138.6 (p-lut), 135.2 (dd, J = 21, 8, C ), 134.7 (dd, J
PC PC
A
2
1
2
JHH = 7.0, 1H, H ), 7.19 (m, 1H, H ), 6.97 (m, 2H, H and H ), 4.15
3, 3, C ), 134.6 (d, J = 12, o-Ph), 133.7 (dd, J = 46, J = 7,
PC
PC
PC
3
F
1
4
(m, 1H, −OCH(CH ) ), 3.65 (s, 6H, −OCH ), 0.73 (d, J = 5.0,
C ), 131.5 (d, J = 53, ipso-Ph), 130.9 (d, J = 2, p-Ph), 130.3 (dd,
JPC = 15, 3, C ), 129.7 (dd, J = 20, 6, C ), 128.9 (d, J = 11, m-
3
2
3
HH
13
PC
PC
3
1
C
B
3
6H, −OCH(CH ) ), 0.12 (d, J = 2.5, 3H, Pd−CH ). C{ H}
3
2
PH
3
PC
PC
2
K
4
2
NMR (CD Cl ): δ 161.1 (d, J = 3.1, C ), 150.8 (o-py), 143.4 (dd,
Ph), 122.9 (d, J = 3, m-lut), 60.2 (d, J = 5, −OCH CH ), 26.5
2
2
PC
PC
PC
2
3
1
2
E
J
3
2
JPC = 165, J = 20.1, C ), 138.2 (p-py), 137.1 (br, C ), 134.3 (dd,
(
lut−CH ), 16.1 (d, J = 7, −OCH CH ), −5.2 (d, J = 4, Pd−
PC
3
PC
2
3
PC
D
2
A
H
CH ). ESI-MS (CH Cl /MeOH, 1:1 by volume, positive scan, m/z):
J
PC = 18.7, 7.7, C ), 134.0 (d, JPC = 8.4, C ), 133.2 (C ), 131.8 (dd,
3
2
2
+
+
1
2
F
3
C
3
5
98.2 [MH] . HRMS: calcd. for [C H P O NPd] , m/z 598.0892.
JPC = 52, JPC = 8.3, C ), 129.7 (d, JPC = 12.1, C ), 128.3 (d, JPC =
28
32
2
3
B
2
G
1
Found: 598.0897.
7.0, C ), 125.1 (m-py), 120.9 (d, J = 10.7, C ), 118.7 (d, J = 54,
PC PC
2
L
4
I
2
(
κ -P,O-1-PPh -2-PO Et-Ph)PdMe(pyridine) (2b-py). 2b-py
was synthesized using a similar procedure to 2a-lut with (TMEDA)-
PdMe (0.055 g, 0.22 mmol), H[1b] (0.082 g, 0.22 mmol), pyridine
0.05 mL, 0.6 mmol), and CH Cl (10 mL). 2b-py was obtained as a
C ), 111.7 (d, J = 4.4, C ), 67.8 (d, J = 5.5, −OCH(CH ) ), 55.6
2
3
PC
PC
3 2
3
(−OCH ), 23.9 (d, JPC = 3.3, −OCH(CH ) ), 0.31 (Pd−CH ).
3
3
2
3
+
HRMS calc. for [C H NO P Pd] m/z 644.09472. Found: 644.0936.
2
29 34 5 2
2
(
(κ -1-PPh -2-P(O)(O-B(C F ) )Ph-Ph)PdMe(2,6-lutidine) (3a-
2 6 5 3
2
2
3
1
1
3
pale yellow solid (0.040 g, 32%). P{ H} NMR (CDCl ): 32.1 (d, J
lut). A vial was charged with 2a-lut (0.203 g, 0.296 mmol), B(C
(0.184 g, 0.359 mmol), and CH Cl (3 mL). The resulting yellow
solution was stirred in the dark at room temperature for 1 h. The
stirring was terminated, pentane was layered onto the CH Cl , and the
6 5 3
F )
3
PP
3
1
=
15, PO), 10.4 (d, J = 15, P−Pd). H NMR (CDCl ): 8.85 (2H,
2
2
PP
3
D
3
o-py), 8.19 (m, 1H, H ), 7.86 (t, J = 7, 1H, p-py), 7.58−7.38 (m,
HH
C
3
B
1
1
7
3H, H , m-py, Ph signals), 7.34 (td, J = 7.6, 1.4, 1H, H ), 7.02 (m,
2
2
HH
A
3
3
3
H, H ), 3.35 (dq, J = J = 7, 2H, −OCH CH ), 0.66 (t, J
=
mixture was stored at −40 °C for 20 h, after which a white solid had
formed. The solid was collected, rinsed with pentane, and dried under
vacuum. The crude solid was purified by Soxhlet extraction into
cyclohexane, washed with hexanes, and dissolved in minimum CH Cl .
HH
PH
2
3
HH
3
13
1
, 3H, −OCH CH ), 0.28 (d, J = 2.5, 3H, Pd−CH ). C{ H}
2
3
PH
3
2
NMR (CD Cl ): δ 150.5 (o-py), 138.6 (p-py), 135.3 (d, J = 10.3,
2
2
PC
D
A
2
C ), 134.8 (obscured by o-Ph, C ), 134.7 (d, J = 12, o-Ph), 133.4
PC
2
2
F
C
B
(
C ), 131.4 (ipso-Ph), 131.0 (p-Ph), 130.4 (C ), 129.7 (C ), 128.9 (d,
Hexanes was added to precipitate 3a-lut as a white solid, which was
J
Organometallics XXXX, XXX, XXX−XXX