Monoarylated Fluoromesitylpalladium Complexes
FULL PAPER
ppm. C21H14N2ClF9Pd (607.2): calcd. C 41.54, H 2.32, N 4.61;
found C 41.58, H 2.44, N 4.64.
room temperature. n-Hexane (10 mL) was then added and the di-
chloromethane evaporated off to give a yellow solid that was
washed with n-hexane (3 ϫ 5 mL), vacuum dried and recrystallized
from dichloromethane/hexane [yield: 0.073 g (73%)]. IR: ν˜ ϭ 1616
m, 1571 w (sh), 1406 w, 1299 s, 1284 vs, 1262 s, 1185 vs, 1144 s,
1118 vs (sh), 1083 m, 1024 m, 924 w, 907 m, 853 vw, 834 m, 753
m, 744 s, 693 m, 684 m, 666 vw, 506 vw, 478 w, 467 vw, 455 vw,
[PdCl(Fmes)(biquinolyl)] (3c): 2,2Ј-Biquinolyl (0.056 g, 0.22 mmol)
was added to a yellow solution of 1a (0.093 g, 0.1 mmol) in di-
chloromethane (15 mL) and stirred for 7 h at room temperature to
give a cloudy solution. The volatiles were then pumped off and the
yellow residue was washed with n-hexane (3 ϫ 5 mL) and vacuum
dried to furnish 0.109 g (80%) of 3c. IR: ν˜ ϭ 1619 m, 1600 m, 1575
w, 1344 m, 1300 s, 1282 vs, 1265 s, 1188 vs, 1131 vs (br), 1083 m,
1031 m, 992 w, 972 w, 915 m, 872 w, 855 w, 830 s, 784 m, 750 s,
1
436 vw, 322 w cmϪ1. H NMR: δ ϭ 8.04 (m, C6H5, 2 H), 7.76 [s,
C6H2(CF3)3, 2 H], 7.51 (m, C6H5, 3 H), 7.47 (m, C6H5, 5 H), 3.32
(m, CH2, 2 H), 3.09 (m, CH2, 2 H) ppm. 19F NMR: δ ϭ Ϫ57.78 (s,
ortho-CF3, 6 F), Ϫ63.22 (s, para-CF3, 3 F) ppm. C23H16ClF9PdS2
(669.3): calcd. C 41.27, H 2.41; found C 41.00, H 2.42.
684 m, 506 vw, 490 vw, 470 vw, 439 vw, 328 w cmϪ1 1H NMR:
.
δ ϭ 9.37 [d, J ϭ 8.2 Hz, (NC9H6)2, H6 cis to Cl, 1 H], 8.57 [t, J ϭ
8.8 Hz, (NC9H6)2, 2 H], 8.35 [d, J ϭ 8.7 Hz, (NC9H6)2, 1 H], 8.25
[d, J ϭ 8.8 Hz, (NC9H6)2, 1 H], 7.93 [m, (NC9H6)2, 2 H], 7.85 [d,
J ϭ 7.8 Hz, (NC9H6)2, 1 H], 7.73 [m, C6H2(CF3)3 and (NC9H6)2,
4 H], 7.49 [m, (NC9H6)2, 2 H] ppm. 19F NMR: δ ϭ Ϫ58.44 (s,
ortho-CF3, 6 F), Ϫ63.01 (s, para-CF3, 3 F) ppm. C27H14N2ClF9Pd
(679.3): calcd. C 47.73, H 2.08, N 4.12; found C 47.56, H 2.12,
N 4.10.
[PdCl(Fmes)(dppe)] (3g): The ligand dppe (0.040 g, 0.1 mmol) was
added to a solution of 1a (0.047 g, 0.05 mmol) in toluene (10 mL).
The solution was then boiled under reflux for 2 h, after which the
volatiles were pumped off and the resultant white residue was dis-
solved in dichloromethane filtered through dry Celite. Hexane
(10 mL) was then added to the filtrate, which was concentrated
and cooled to Ϫ20 °C. The thus obtained colorless crystals were
decanted, washed with n-hexane (3 ϫ 5 mL) and vacuum dried to
yield 0.052 g (63%) of 3g. IR: ν˜ ϭ 1618 m, 1569 vw, 1438 m, 1298
s, 1279 vs, 1261 s, 1186 vs, 1130 vs (sh), 1106 s, 1079 m, 1021 w,
1000 vw, 925 vw, 890 w, 852 vw, 826 w, 745 s, 706 s, 692 s, 666 w,
530 m, 498 m, 481 w, 439 vw, 329 vw, 298 vw cmϪ1. 1H NMR: δ ϭ
[PdCl(Fmes)(OPPhPy2-N,NЈ)] (3d): OPPhPy2 (0.031 g, 0.11 mmol)
was added to a yellow solution of 1a (0.047 g, 0.05 mmol) in di-
chloromethane (10 mL) and stirred at room temperature for 8 h to
give a colorless solution. n-Hexane was then added and the solution
was concentrated. The resultant white solid was washed with n-
hexane (3 ϫ 5 mL), vacuum dried and recrystallized from dichloro-
methane/hexane to yield 0.045 g (64%) of 3d as colorless crystals.
IR: ν˜ ϭ 1617 s, 1591 m, 1569 w, 1298 vs, 1275 vs, 1217 s, 1194 vs,
1136 vs, 1060 m, 1024 s, 997 w, 928 w, 906 s, 853 m, 835 m, 777 m,
756 s, 744 s, 702 m, 692 s, 684 s, 667 vw, 646 vw, 547 s, 504 w, 471
8.00 (m, C6H5, para-H, 4 H), 7.60 [d, JP
ϭ 1.0 Hz,
H
Fmes
C6H2(CF3)3, 2 H], 7.51 (m, C6H5, 6 H), 7.37 t(rmans, C6H5, 2 H), 7.18
(m, C6H5, 8 H), 2.58 (m, CH2, 2 H), 2.15 (m, CH2, 2 H) ppm. 19F
NMR: δ ϭ Ϫ58.29 (d, JP,F ϭ 5.5 Hz, ortho-CF3, 6 F), Ϫ63.12 (s,
para-CF3, 3 F) ppm. 31P{1H} NMR: δ ϭ 52.9 (d sept., JP,P ϭ 23.2,
JP,F ϭ 5.5 Hz, Pcis of dppe), 39.67 (d, JP,P ϭ 23.2 Hz, Ptrans of dppe)
1
vw, 451 w, 438 vw, 326 vw, 305 vw, 285 vw cmϪ1. H NMR: δ ϭ
ppm. C35H26ClF9P2Pd (821.4): calcd. C 51.18, H 3.19; found C
51.03, H 3.29.
9.69 (d, J ϭ 5.5 Hz, C5H4N, H6 cis to Cl, 1 H), 8.81 (t, J ϭ 7.5 Hz,
C5H4N, H3, 1 H), 8.47 (t, J ϭ 7.0 Hz, C5H4N, H3, 1 H), 8.18 (m,
C5H4N, H4, 1 H), 8.08 (m, C5H4N, H4, 1 H), 7.93 (d, J ϭ 6.5 Hz,
C5H4N, H6, 1 H), 7.92 [s, C6H2(CF3)3, 1 H], 7.80 (m, C6H5, 4 H),
7.71 (m, C5H4N, H5, 1 H), 7.6 (m, H5of C5H4N, and C6H5, 2 H),
7.54 [s, C6H2(CF3)3, 1 H] ppm. 19F NMR: δ ϭ Ϫ57.13 (s, ortho-
CF3, 3 F), Ϫ62.42 (s, ortho-CF3, 3 F), Ϫ63.19 (s, para-CF3, 3 F)
ppm. 31P{1H} NMR: δ ϭ 20.4 (s) ppm. C25H15ClF9N2OPPd
(703.2): calcd. C 42.70, H 2.15, N 3.98; found C 43.04, H 2.35,
N 3.91.
[PdCl(Fmes)(2,6-lut)(NCMe)] (4a): 2,6-Lut (25 µL, 0.023 g,
0.22 mmol) was added to a yellow solution of 1a (0.093 g,
0.1 mmol) in dichloromethane (10 mL) and stirred for 5 h at room
temperature to give a colorless solution, to which n-hexane was
added. This solution was then concentrated and cooled to Ϫ20 °C
to give a white solid that was washed with n-hexane (3 ϫ 5 mL)
and vacuum dried to yield 0.094 g (82%) of 4a. IR: ν˜ ϭ 2343 m,
2303 w, 1616 m, 1583 m, 1571 m, 1300 vs, 1288 vs, 1264 vs, 1180
vs (br), 1119 vs (br), 1095 m, 1029 m, 915 s, 854 m, 837 m, 781 s,
757 m, 695 m, 684 s, 668 vw, 577 vw, 470 vw, 438 w, 374 w, 340 w
[PdCl(Fmes){(OH)(CH3)CPy2-N,NЈ}]
(3e):
(OH)(CH3)CPy2
1
3 4
cmϪ1. H NMR: δ ϭ 7.84 [s, C6H2(CF3)3, 2 H], 7.56 [t, JH H
ϭ
(0.024 g, 0.12 mmol) was added to a yellow solution of 1a (0.047 g,
0.05 mmol) in dichloromethane (10 mL) and stirred at room tem-
perature for 2 h. Then n-hexane was added and the solution con-
centrated. The resultant yellow solid was washed with n-hexane (3
ϫ 5 mL), vacuum dried and recrystallized from dichloromethane/
hexane to yield 0.061 g (88%) of 3e·CH2Cl2 as yellow crystals. IR:
ν˜ ϭ 3371 m, 1619 m, 1603 m, 1569 w, 1283 vs, 1262 s, 1189 vw,
1126 vs, 1097 m, 1083 m, 1060 m, 1027 m, 944 w, 913 m, 854 w,
834 w, 791 w, 761 m, 694 w, 684 m, 667 vw, 654 vw, 590 vw, 468
7.7 Hz, NC5H3(CH3)2, H4, 1 H], 7.11 [d, JH H ϭ 7.7 Hz,
NC5H3(CH3)2, H3, 2 H], 3.29 [s, NC5H3(CH3)2, 6 H], 2.08 (s,
CH3CN, 3 H) ppm. 19F NMR: δ ϭ Ϫ58.22 (s, ortho-CF3, 6 F),
Ϫ63.06 (s, para-CF3, 3 F) ppm. C18H14ClF9N2Pd (571.2): calcd. C
37.85, H 2.47, N 4.90; found C 37.97, H 2.54, N 4.70.
3
4
[PdCl(Fmes)(3,5-lut)(NCMe)] (4b): 3,5-Lut (25 µL, 0.023 g,
0.22 mmol) was added to a yellow solution of 1a (0.093 g,
0.1 mmol) in dichloromethane (10 mL) and stirred for 15 min at
room temperature to give a colorless solution. Then n-hexane was
added and the solution was concentrated and cooled to Ϫ20 °C.
The colorless crystals thus obtained were decanted, washed with n-
hexane (3 ϫ 5 mL) and vacuum dried to yield 0.060 g (53%) of 4b.
IR: ν˜ ϭ 2329 w, 2303 w, 1618 m, 1599 w, 1572 w, 1304 vs, 1292 vs,
1263 s, 1184 vs, 1157 s, 1143 s, 1117 vs, 1084 m, 1032 w, 913 m,
865 w, 856 vw, 835 w, 774 w, 755 w, 700 m, 684 m, 667 vw, 471 vw,
vw, 436 vw, 332 vw cmϪ1 1H NMR ([D6]Me2CO): δ ϭ 9.30 (m,
.
C5H4N, H6 cis to Cl, 1 H), 8.36 (m, C5H4N, 1 H), 8.10 (m, C5H4N,
3 H), 8.01 [s, C6H2(CF3)3, 1 H], 7.91 (m, C5H4N, 1 H), 7.84 [s,
C6H2(CF3)3, 1 H], 7.60 (m, C5H4N, 1 H), 7.23 (m, C5H4N, 1 H),
6.40 (s, OH, 1 H), 3.00 (s, CH3, 3 H) ppm. 19F NMR ([D6]Me2CO):
δ ϭ Ϫ56.17 (br., ortho-CF3, 3 F), Ϫ58.86 (br., ortho-CF3, 3 F),
Ϫ61.96 (s, para-CF3, 3 F) ppm. C22H16Cl3F9N2OPd (708.1): calcd.
C 38.12, H 2.33, N 4.05; found C 38.08, H 2.34, N 3.94.
1
439 vw, 344 vw cmϪ1. H NMR: δ ϭ 8.35 [s, NC5H3(CH3)2, H2, 2
[PdCl(Fmes)(pte)]
(3f):
1,2-Bis(phenylthio)ethane
(0.041 g,
H], 7.80 [s, C6H2(CF3)3, 2 H], 7.42 [s, NC5H3(CH3)2, H4, 1 H], 2.35
[s, NC5H3(CH3)2, 6 H], 2.14 (s, CH3CN, 3 H) ppm. 19F NMR:
δ ϭ Ϫ58.48 (s, ortho-CF3, 6 F), Ϫ63.04 (s, para-CF3, 3 F) ppm.
0.165 mmol) was added to a yellow solution of 1a (0.067 g,
0.075 mmol) in dichloromethane (10 mL) and stirred for 5 h at
Eur. J. Inorg. Chem. 2003, 3127Ϫ3138
2003 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim
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