Organometallics
Article
temperature to yield a solution of lithium [chloro(phenyl)phosphino]-
benzenesulfonate. 1-Bromo-2-methoxybenzene (1.86 g, 10 mmol) was
dissolved in dry THF (20 mL) under nitrogen and cooled to −78 °C
(162 MHz, DMSO): δ −10.90. ESI-MS (m/z): [M − H]− calcd for
C24H18O5PS2, 481.0328; found, 481.0330. Anal. Calcd for
C24H19O5PS2: C, 59.74; H, 3.97; Found: C, 60.02; H, 4.23.
n
in a separate Schlenk. BuLi (2.5 M in hexane, 4 mL, 10 mmol) was
Preparation of Catalyst Pd1. (TMEDA)PdMe2 (136 mg, 0.54
mmol) was added to a suspension of Ligand L1 (200 mg, 0.54 mmol)
in dioxane (5 mL) at room temperature. After 5 min, the evolution of
gas stopped and the suspension turned clear. The solution was stirred
for 1 h at room temperature. The resulting white precipitate was
filtered, washed with diethyl ether, and dried under reduced pressure
to yield the tmeda-bridged dimer 1-TMEDA according to the
literature.4 1-TMEDA was dispersed in 5 mL of DMSO at room
temperature. The solvent was removed under reduced pressure at 70
°C. After removal of DMSO under reduced pressure, the resulting
solid was dispersed in diethyl ether, and isolated by filtration to yield a
white solid (208 mg, 70%). 1H NMR (400 MHz, CDCl3): δ 8.22 (dd,
J = 7.1, 4.6 Hz, 1H), 7.64 (dd, J = 12.3, 7.0 Hz, 2H), 7.56−7.40 (m,
5H), 7.34 (t, J = 7.6 Hz, 1H), 7.12 (dd, J = 10.8, 7.8 Hz, 1H), 6.95 (dd,
J = 8.9, 4.7 Hz, 3H), 3.72 (s, 3H, MeO), 3.03 (s, 6H, DMSO-H), 0.46
(s, 3H, Pd-CH3). 13C NMR (100 MHz, CDCl3): δ 160.02 (d, J = 4.2
Hz), 148.16 (d, J = 14.1 Hz), 135.16 (d, J = 5.9 Hz), 134.83 (d, J =
12.9 Hz), 133.37 (d, J = 30.9 Hz), 131.01 (d, J = 22.8 Hz), 129.77 (d, J
= 7.1 Hz), 128.71 (d, J = 11.6 Hz), 128.51 (d, J = 8.1 Hz), 128.42 (s),
128.25 (s), 127.80 (d, J = 9.4 Hz), 120.77 (d, J = 9.9 Hz), 117.87 (s),
117.29 (s), 111.59 (d, J = 4.6 Hz), 55.80 (s, MeO), 40.96 (s, DMSO),
1.74 (s, Pd-CH3). 31P NMR (162 MHz, DMSO): δ 21.32. Anal. Calcd
for C22H25O5PPdS2: C, 46.28; H, 4.41. Found: C, 45.91; H, 4.23.
Preparation of Catalyst Pd2. A procedure similar to that for Pd1
was employed except L2 (200 mg, 0.47 mmol) was used. Pd2 was
obtained as a white solid (208 mg, 70%). 1H NMR (400 MHz,
CDCl3): δ 8.23−8.13 (m, 1H), 7.72 (dd, J = 12.2, 7.4 Hz, 2H), 7.48
(dt, J = 14.9, 7.7 Hz, 5H), 7.34 (t, J = 7.4 Hz, 1H), 7.26−7.17 (m, 4H),
7.15−7.04 (m, 2H), 6.91 (dd, J = 7.8, 5.0 Hz, 1H), 6.82 (d, J = 7.9 Hz,
2H), 2.82 (s, 6H, DMSO-H), 0.56 (s, 3H, Pd-CH3). 13C NMR (100
MHz, CDCl3): δ 158.16 (d, J = 4.2 Hz), 155.20 (s), 148.15 (d, J = 14.4
Hz), 135.66 (d, J = 6.1 Hz), 134.99 (d, J = 12.9 Hz), 133.78 (s),
133.28 (s), 131.44 (s), 131.06 (s), 129.95 (s), 128.93 (d, J = 11.7 Hz),
128.49 (d, J = 8.1 Hz), 128.25 (s), 127.76 (s), 124.33 (s), 122.99 (d, J
= 9.6 Hz), 120.69 (s), 120.13 (s), 119.40 (s), 117.57 (d, J = 4.5 Hz),
40.96 (s, DMSO), 2.72 (s, Pd-CH3). 31P NMR (162 MHz, DMSO): δ
21.49. Anal. Calcd for C27H27O5PPdS2: C, 51.23; H, 4.30. Found: C,
50.85; H, 4.80.
Preparation of Catalyst Pd3. A procedure similar to that for Pd1
was employed except L3 (200 mg, 0.43 mmol) was used. Pd3 was
obtained as a white solid (211 mg, 72%). 1H NMR (400 MHz,
CDCl3): δ 8.21 (br, 1H), 7.82 (br, 2H), 7.49 (br, 4H), 7.32 (d, J =
42.2 Hz, 4H), 7.00 (d, J = 16.0 Hz, 4H), 6.39 (s, 1H), 2.94 (s, 6H,
DMSO-H), 2.14 (s, 3H, Ph-Me), 1.61 (s, 3H, Ph-Me), 0.61 (s, 3H, Pd-
CH3). 13C NMR (100 MHz, CDCl3): δ 157.86 (s), 150.14 (s), 148.20
(d, J = 16.5 Hz), 135.38 (d, J = 11.8 Hz), 134.07 (s), 133.39 (s),
131.31 (s), 130.96 (s), 130.02 (s), 129.28 (s), 129.07 (s), 128.75 (d, J
= 11.6 Hz), 128.46 (s), 128.15 (s), 127.76 (s), 127.20 (s), 125.63 (s),
121.18 (d, J = 8.1 Hz), 116.99 (d, J = 55.2 Hz), 112.53 (s), 40.75 (s,
DMSO), 17.34 (s, Ph-Me), 16.66 (s, Ph-Me), 2.74 (s, Pd-Me). 31P
NMR (162 MHz, DMSO): δ 20.66. Anal. Calcd for C29H31O5PPdS2:
C, 52.69; H, 4.73. Found: C, 53.16; H, 4.54.
Preparation of Catalyst Pd4. A procedure similar to that for Pd1
was employed except L4 (200 mg, 0.41 mmol) was used. Pd4 was
obtained as a white solid (173 mg, 65%). 1H NMR (400 MHz,
CDCl3): δ 8.28 (br, 1H), 7.98 (br, 1H), 7.73 (br, 2H), 7.67−7.38 (m,
10H), 7.30 (d, J = 7.7 Hz, 2H), 7.14−7.06 (m, 1H), 7.01 (d, J = 9.3
Hz, 1H), 2.89 (s, 6H, DMSO-H), 0.55 (s, 3H, Pd-CH3). 13C NMR
(100 MHz, CDCl3): δ 147.38 (d, J = 15.3 Hz), 143.74 (d, J = 8.3 Hz),
140.98 (s), 135.80 (d, J = 5.2 Hz), 133.78 (s), 133.45 (d, J = 5.9 Hz),
133.10 (s), 132.27 (d, J = 7.3 Hz), 131.71 (s), 131.06 (s), 130.94 (s),
130.48 (s), 129.82 (d, J = 6.6 Hz), 129.47 (s), 129.29 (s), 129.16 (s),
128.98 (s), 128.90 (s), 128.66 (s), 128.09 (s), 41.30 (s, DMSO), 0.11
(s, Pd-CH3). 31P NMR (162 MHz, DMSO): δ 31.87. Anal. Calcd for
C27H27O6PPdS3: C, 47.61; H, 4.00. Found: C, 47.36; H, 3.85.
Preparation of Catalyst Ni1. A suspension of L1 (100 mg, 0.27
mmol) and Na2CO3 (86 mg, 0.81 mmol) in 10 mL of CH2Cl2 was
added dropwise. The resulting solution was stirred for 1.0 h at −78 °C
before the lithium [chloro(phenyl)phosphino]benzenesulfonate sol-
ution was added dropwise. The mixture was stirred for another 24 h at
room temperature. The volatiles were removed, and the residue was
taken up in distilled water. The mixture was acidified with
concentrated HCl/H2O solution and extracted three times with
CH2Cl2 (75 mL). The extracts were combined, dried over MgSO4, and
concentrated under vacuum. The crude product was recrystallized
from dichloromethane/ether at room temperature. The resulting white
powder was filtered and dried to give L1 (2.2 g, 60%). 1H NMR (400
MHz, CDCl3): δ 8.41−8.31 (m, 1H), 7.80−7.75 (m, 1H), 7.72 (dd, J
= 16.2, 5.1 Hz, 2H), 7.54 (dd, J = 13.0, 5.9 Hz, 4H), 7.50−7.44 (m,
1H), 7.21 (dd, J = 14.7, 7.7 Hz, 1H), 7.17−7.05 (m, 3H), 3.77 (d, J =
11.9 Hz, 3H). 13C NMR (100 MHz, CDCl3): δ 161.24 (d, J = 1.9 Hz),
152.20 (d, J = 8.9 Hz), 137.25 (d, J = 1.4 Hz), 134.98 (d, J = 8.0 Hz),
134.80 (d, J = 2.8 Hz), 134.26 (d, J = 11.7 Hz), 134.07 (d, J = 2.9 Hz),
132.73 (d, J = 11.3 Hz), 129.84 (d, J = 13.0 Hz), δ 129.77 (d, J = 13.5
Hz). 128.82 (d, J = 9.2 Hz), 122.03 (d, J = 13.2 Hz), 118.27 (d, J =
91.0 Hz), 112.79 (d, J = 96.9 Hz), 112.04 (d, J = 6.1 Hz), 105.86 (d, J
= 93.9 Hz), 56.43 (s). 31P NMR (162 MHz, CDCl3): δ −2.83 (s). ESI-
MS (m/z): [M − H]− calcd for C19H16O4PS, 371.0501; found,
371.0517. Anal. Calcd for C19H17O4PS: C, 61.28; H, 4.60. Found: C,
61.08; H, 4.54.
Preparation of Ligand L2. A procedure similar to that for L1 was
employed except 2-bromodiphenyl ether (2.49 g, 10 mmol) was used.
1
L2 was obtained as a white solid (2.8 g, 65%). H NMR (400 MHz,
CDCl3): δ 8.39 (dd, J = 7.2, 5.1 Hz, 1H), 7.84−7.71 (m, 2H), 7.70−
7.57 (m, 5H), 7.49 (m, 1H), 7.41−7.26 (m, 4H), 7.26−7.14 (m, 2H),
6.96−6.82 (m, 3H). 13C NMR (100 MHz, CDCl3): δ 160.27 (d, J =
1.8 Hz), 153.93 (s), 152.79 (d, J = 9.0 Hz), 136.71 (d, J = 2.0 Hz),
135.25 (s), 135.17 (s), 134.75 (d, J = 12.1 Hz), 134.37 (d, J = 2.9 Hz),
133.15 (d, J = 11.3 Hz), 130.21 (s), 130.04 (d, J = 13.3 Hz), 129.84 (d,
J = 13.2 Hz), 129.31 (d, J = 9.3 Hz), 125.72 (s), 123.92 (d, J = 13.4
Hz), 120.27 (s), 119.01 (d, J = 88.5 Hz), 116.67 (d, J = 6.2 Hz),
112.38 (d, J = 97.3 Hz), 108.48 (d, J = 97.5 Hz). 31P NMR (162 MHz,
CDCl3): δ −1.14. ESI-MS (m/z): [M − H]− calcd for C24H18O4PS,
433.0658; found, 433.0660. Anal. Calcd for C24H19O4PS: C, 66.35; H,
4.41. Found: C, 65.98; H, 4.37.
Preparation of Ligand L3. A procedure similar to that for L1 was
employed except 2-(2-bromophenoxy)-1,3-dimethylbenzene (2.77 g,
10 mmol) was used. L3 was obtained as a white solid (2.3 g, 50%). 1H
NMR (400 MHz, CDCl3): δ 8.46−8.36 (m, 1H), 7.83−7.73 (m, 2H),
7.72−7.57 (m, 4H), 7.52 (dd, J = 15.0, 6.9 Hz, 2H), 7.39−7.26 (m,
2H), 7.23 (d, J = 7.0 Hz, 1H), 7.19−7.11 (m, 1H), 7.05 (d, J = 5.5 Hz,
1H), 6.99 (d, J = 5.3 Hz, 1H), 6.49 (t, J = 7.2 Hz, 1H), 2.01 (s, 3H,
CH3), 1.63 (s, 3H, CH3). 13C NMR (100 MHz, CDCl3): δ 158.70 (s),
151.97 (d, J = 9.0 Hz), 148.78 (s), 136.57 (s), 134.75 (d, J = 12.5 Hz),
134.49 (d, J = 7.5 Hz), 134.20 (s), 132.93 (d, J = 11.2 Hz), 130.43 (d, J
= 52.9 Hz), 129.89 (s), 129.80 (s), 129.68 (s), 129.10 (s), 128.76 (s),
128.69 (d, J = 9.7 Hz), 125.94 (s), 122.57 (d, J = 13.0 Hz), 118.36 (d, J
= 86.9 Hz), 111.91 (d, J = 91.3 Hz), 105.89 (d, J = 95.7 Hz), 15.86 (s,
CH3), 15.42 (s, CH3). 31P NMR (162 MHz, CDCl3): δ −2.25. ESI-
MS (m/z): [M − H]− calcd for C26H22O4PS, 461.0971; found:
461.0983. Anal. Calcd for C26H23O4PS: C, 67.52; H, 5.01. Found: C,
67.23; H, 4.87.
Preparation of Ligand L4. A procedure similar to that for L1 was
employed except 1-bromo-2-(phenylsulfonyl)benzene (2.97 g, 10
1
mmol) was used. L4 was obtained as a white solid (3.0 g, 62%). H
NMR (400 MHz, CDCl3): δ 8.39 (dd, J = 7.7, 4.4 Hz, 1H), 8.18 (d, J
= 7.5 Hz, 2H), 8.05−7.96 (m, 1H), 7.87−7.70 (m, 3H), 7.69−7.53 (m,
6H), 7.53−7.39 (m, 3H), 7.35−7.27 (m, 1H), 7.03 (m, 1H). 13C
NMR (100 MHz, DMSO): δ 151.80 (d, J = 26.5 Hz), 144.17 (d, J =
23.4 Hz), 141.50 (s), 140.47 (s), 140.17 (d, J = 8.5 Hz), 140.05 (s),
136.06 (s), 134.92 (s), 134.16 (d, J = 28.8 Hz), 133.45 (s), 133.26 (s),
133.03 (s), 130.23 (s), 129.21 (s), 128.98 (s), 128.51 (s), 128.45 (s),
128.29 (d, J = 6.3 Hz), 128.04 (s), 127.58 (d, J = 2.8 Hz). 31P NMR
E
Organometallics XXXX, XXX, XXX−XXX