Organometallics
Article
1
3
1
=
6.4 Hz, C-4), 111.1 (d, J = 20.2 Hz, C-3), 67.7 (CH ), 52.9 (NCH ),
2.18 (s, 6H, NCH ), 2.00 (s, 6H, CH CO). C{ H} NMR (126 MHz,
3 3
2
3
19
5
1.6 (NCH ), 24.6 (CH CO). F NMR (471 MHz, CDCl ): δ
CDCl ): δ 182.1 (CO), 167.7 (dd, J = 242.6, 11.2 Hz, C-5), 161.4 (dd,
3
3
3
3
−1
−
115.01 (dd, J = 9.7, 5.5 Hz). IR (ATR, ν cm ): 1601 (m), 1576 (s),
J = 243.2, 11.9 Hz, C-3), 150.1 (dd, J = 17.2, 8.2 Hz, C-6), 119.1 (dd, J
= 34.3, 3.2 Hz, C-1), 105.1 (dd, J = 21.1, 3.3 Hz, C-2), 101.6 (dd, J =
32.2, 23.7, C-4), 73.5 (d, J = 3.1 Hz, CH ), 52.6 (NCH ), 51.6
1
8
558 (s), 1455 (m), 1410 (s), 1345 (m), 1232 (s), 1127 (w), 986 (w),
74 (m), 844 (m), 769 (s), 678 (s). LRMS (LIFDI): m/z 636.02
2
3
+
19
(
100%, [M] ). Anal. Calcd for C H F N O Pd : C, 41.58; H, 4.39;
(NCH ), 23.7 (d, J = 1.7 Hz, CH CO). F NMR (376 MHz, CDCl ):
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28
2
2
4
2
3
3
3
N, 4.22. Found: C, 41.59; H, 4.44; N, 4.51.
δ −100.78 to −100.85 (m, 2F), − 116.37 (dd, J = 17.6, 8.2 Hz, 2F).
+
Acetato-κO-[o-dimethylaminomethyl-3-fluorophenyl-C,N)-
LRMS (LIFDI): m/z 671.99 (100%, [M] ). Anal. Calcd for
(
pyridine-d )palladium(II) (2cpyr2,6). A portion of the mixture of
C H F N O Pd : C, 39.36; H, 3.90; N, 4.17. Found: C, 39.28; H,
5
22 26
4
2
4
2
isomers of di-μ-acetatobis[o-dimethylaminomethyl-3-fluorophenyl-
3.89; N, 3.90.
C,N)dipalladium(II) (2c) was dissolved in pyridine-d to obtain the
Di-μ-chlorobis[o-dimethylaminomethyl-phenyl-C,N)dipalladium-
(II) (3a). Complex 3a was prepared according to general procedure D,
on a 1.69 mmol scale, to afford the product as a yellow powder (462
5
1
two isomers of 2c. H NMR (400 MHz, CDCl ): δ 7.07 (td, J = 5.5,
3
7
6
2
.7 Hz, 1H), 6.90 (m, 2H), 6.77 (m, 1H), 6.65 (t, J = 8.4 Hz, 1H),
1
.28 (dd, J = 8.4, 6.2 Hz, 1H), 3.93 (s, 2H), 3.86 (s, 2H), 2.84 (s, 6H),
mg, 46%). Mp: 173−175 °C (dec) (lit. 183−185 °C). H NMR (500
.76 (s, 6H), 2.19 (s, 6H). 19F NMR (376 MHz, CDCl ): δ −100.98
MHz, CDCl ): δ 7.17 (dd, J = 19.3, 7.6 Hz, 2H), 6.99−6.94 (m, 2H),
3
3
(
dd, J = 8.7, 5.4 Hz), −119.88 (dd, J = 15.9, 9.6 Hz).
6.87 (t, J = 6.8 Hz, 4H), 3.93 (s, 4H), 2.87 (s, 6H), 2.84 (s, 6H). IR
−1
Di-μ-acetatobis[o-dimethylaminomethyl-3-p-fluorophenyl-C,N)-
(ATR, ν cm ): 1738 (w), 1578 (w), 1447 (m), 1259 (s). 1095 (s, br),
dipalladium(II) (2c ). Complex 2c was prepared according to general
1043 (s), 1017 (s, br), 982 (m), 861 (m), 799 (s), 733 (s), 698 (m).
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6
−1
procedure C, on a 0.17 mmol scale, to afford the product as a yellow
Far-IR (ATR, ν cm ): 516.04 (m), 498.64 (w), 477.33 (w), 422.85
(m), 398.60 (w), 368.37 (w), 329.15 (m), 280.00 (m), 265.76 (m),
247.08 (s), 244.39 (m), 232.86 (w), 217.42 (s). LRMS (LIFDI): m/z
1
powder (105.4 mg, 98%). Mp: 191−195 °C (dec). H NMR (500
MHz, CDCl ): δ 6.95 (dd, J = 8.3, 6.2 Hz, 2H, H-1), 6.71−6.61 (m,
3
+
21b
4
H, H-2, H-4), 3.52 (d, J = 13.9 Hz, 2H, CHH′), 3.09 (d, J = 13.9 Hz,
551.96 (100%, [M] ). All data are in accordance with the literature.
2
H, CHH′), 2.79 (s, 6H, NCH ), 2.06 (s, 6H, NCH ), 2.05 (s, 6H,
Di-μ-chlorobis[o-dimethylaminomethyl-2-m-fluorophenyl-C,N)-
dipalladium(II) (3b). Complex 3b was prepared according to general
procedure B, on a 0.26 mmol scale, to afford the product in a mixture
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3
13
1
CH CO). C{ H} NMR (126 MHz, CDCl ): δ 181.1 (CO), 161.3
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3
(
d, J = 240.6 Hz, C-3), 147.7 (d, J = 6.2 Hz, C-1), 137.2 (d, J = 2.5 Hz,
C-6), 133.0 (d, J = 6.8 Hz, C-5), 111.5 (d, J = 19.7 Hz, C-4), 108.6 (d,
J = 21.4 Hz, C-2), 72.0 (CH ), 52.7 (NCH ), 51.3 (NCH ), 24.6
of geometrical isomers (syn and anti) as a yellow powder (74 mg,
1
86%). Mp: 180−182 °C (dec). H NMR (500 MHz, CDCl
): δ 6.94
2
3
3
3
19
(
CH CO). F NMR (471 MHz, CDCl ): δ − 119.31 (td, J = 9.6, 6.2
(dd, J = 20.1, 7.7 Hz, 2H), 6.70 (dd, J = 13.6, 4.9 Hz, 2H), 6.87 (td J =
3
3
+
Hz). LRMS (LIFDI): m/z 636.00 (100%, [M] ). Anal. Calcd for
C H F N O Pd ·0.2AgCl: C, 39.8; H, 4.25; N, 4.22. Found: C,
7.9, 5,6 Hz, 2H), 4.01 (d, J = 2.3 Hz, 4H), 2.88 (s, 6H), 2.86 (s, 6H).
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1
C{ H} NMR (126 MHz, CDCl ): δ 156.1 (J = 249.6, 2.4 Hz), 144.9
2
2
28
2
2
4
2
3
3
9.87; H, 4.26; N, 3.97.
Di-μ-acetatobis[o-dimethylaminomethyl-2,5-o,m-difluorophen-
(d, J = 13.12 Hz), 132.8 (t, J = 11.1 Hz), 128.8 (dd, J = 67.6, 2.9 Hz),
126.5 (dd, J = 13.4, 6.6 Hz), 111.6 (d, J = 20.2 Hz), 68.6 (d, J = 22.3
Hz), 53.3, 53.0. 19F NMR (376 MHz, CDCl ): δ −113.91 to −114.05
yl-C,N)dipalladium(II) (2d). Complex 2d was prepared according to
general procedure A, on a 0.26 mmol scale, to afford the product as a
yellow-green powder (70.2 mg, 78%). Mp: 187−190 °C (dec). H
NMR (400 MHz, CDCl ): δ 6.67 (td, J = 8.7, 3.7 Hz, 2H, H-3), 6.51
3
+
(m). LRMS (LIFDI): m/z 587.92 (100%, [M] ). Anal. Calcd for
1
C H F N Cl Pd : C, 36.76; H, 3.77; N, 4.76. Found: C, 36.63; H,
18 22 2 2 2 2
3
3.64; N, 4.40.
(
3
td, J = 7.7, 4 Hz, 2H, H-4), 3.76 (dd, J = 14.4, 1.8 Hz, 2H, CHH′),
Di-μ-chlorobis[o-dimethylaminomethyl-3-p-fluorophenyl-C,N)-
.54 (d, J = 14.4 Hz, 2H, CHH′), 2.83 (s, 6H, NCH ), 2.23 (s, 6H,
dipalladium(II) (3c ). Complex 3c was prepared according to general
3
6
6
13
1
NCH ), 2.00 (s, 6H, CH CO). C{ H} NMR (126 MHz, CDCl ): δ
procedure B, on a 0.77 mmol scale, to afford the product in a mixture
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1
82.2 (CO), 163.6 (dd, J = 235.5, 1.8 Hz, C-5), 153.1 (dd, J = 244.9,
of geometrical isomers (syn and anti) as a yellow powder (171 mg,
1
2
.2 Hz, C-2), 134.7 (dd, J = 15.1, 12.4 Hz, C-1), 127.9 (d, J = 36.9 Hz,
76%). Mp: 174.4−176.2 °C (dec). H NMR (500 MHz, CDCl ): δ
3
C-6), 114.5 (dd, J = 31.5, 7.6 Hz, C-4), 112.1 (dd, J = , 23.4, 8.6 Hz, C-
), 69.0 (CH ), 52.8 (NCH ), 51.9 (NCH ), 23.6 (d, J = 2.1 Hz,
7.17−6.98 (m, 2H), 6.65 (d, J = 9.2 Hz, 4H), 3.90 (br s, 4H), 2.86 (s,
6H), 2.83 (s, 6H). 13C{ H} NMR (126 MHz, CDCl ): δ 161.4 (d, J =
1
3
2
3
3
3
19
CH CO). F NMR (376 MHz, CDCl ): δ −111.12 (ddd, J = 20.9,
241.5 Hz, major), 161.4 (d, J = 241.6 Hz, minor isomer), 147.6 (d, J =
6.3 Hz, major isomer), 147.6 (d, J = 6.5 Hz, minor isomer), 136.1 (d, J
= 2.2 Hz, major isomer), 136.0 (d, J = 2.2 Hz, minor isomer), 133.8 (d,
J = 6.9 Hz, major isomer), 134.3 (d, J = 7.0 Hz, minor isomer), 112.0
(d, J = 9.8 Hz, major isomer), 111.9 (d, J = 9.8 Hz, minor isomer),
109.0 (s, major isomer), 108.8 (s, minor isomer), 73.2 (d, J = 2.6 Hz,
major isomer), 73.0 (d, J = 2.9 Hz, major isomer), 53.1 (s, major
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3
−1
7
1
.6, 3.6 Hz, 2F), −120.86 to −121.28 (m, 2F). IR (ATR, ν cm ):
590 (s), 1571 (s), 1458 (s), 1418 (s, br), 1349 (m), 1213 (s), 1023
(
m), 972 (m), 838 (s), 805 (s), 727 (s), 683 (m). LRMS (LIFDI): m/
+
z 672.02 (100%, [M] ). Anal. Calcd for C H F N O Pd : C, 39.36;
H, 3.90; N, 4.17. Found: C, 38.99; H, 3.91; N, 4.31.
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Di-μ-acetatobis[o-dimethylaminomethyl-3,4-p,m-difluorophen-
isomer), 52.8 (s, minor isomer). 19F NMR (471 MHz, CDCl ): δ
yl-C,N)dipalladium(II) (2e ). Complex 2e was prepared according to
general procedure C, on a 0.16 mmol scale, to afford the product as a
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−119.01 (dd, J = 15.4, 9.4 Hz, syn isomer), −119.10 (dd, J = 15.4, 9.2
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−1
yellow powder (102 mg, 95%). Mp: 188−190 °C (dec). H NMR
Hz, anti isomer). Far-IR (ATR, ν cm ): 576.72 (m), 553.97 (w),
(
500 MHz, CDCl ): δ 6.78−6.72 (m, 4H, H-2, H-5), 3.58 (d, J = 13.8
518.76 (w), 441.67 (m), 427.53 (m), 337.55 (m), 316.09 (s), 274.60
(m), 255.36 (w), 252.25 (w), 239.54 (s), 215.26 (s), 196.34 (m).
3
Hz, 2H, CHH′), 3.13 (d, J = 13.8 Hz, 2H, CHH′), 2.79 (s, 6H,
NCH ), 2.11 (s, 6H, NCH ), 2.06 (s, 6H, CH CO). C{ H} NMR
13
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+
3
3
3
LRMS (LIFDI): m/z 587.89 (100%, [M] ). Anal. Calcd for
(
126 MHz, CDCl ): δ 181.6 (CO), 148.3 (dd, J = 243.2, 13.7 Hz, C-
C H F N Cl Pd : C, 36.76; H, 3.77; N, 4.76. Found: C, 36.61; H,
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2
2
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), 146.7 (dd, J = 250.6, 12.1 Hz, C-4), 142.0 (dd, J = 4.8, 3.7 Hz, C-
), 138.9 (dd, J = 3.7, 2.9 Hz, C-1), 120.0 (d, J = 14.7 Hz, C-5), 110.3
3.77; N, 4.53.
Chloro-κO-[o-dimethylaminomethyl-3-p-fluorophenyl-C,N)-
(
d, J = 17.5 Hz, C-2), 72.0 (CH ), 52.6 (NCH ), 51.5 (NCH ), 24.6
(pyridine-d )palladium(II) (3c ). A portion of di-μ-chlorobis[o-
2 3 3
5
6pyr
19
(
CH CO). F NMR (471 MHz, CDCl ): δ −140.86 to −141.00 (m,
dimethylaminomethyl-3-p-fluorophenyl-C,N)dipalladium(II) (3c )
3
3
6
1
2
6
3
F), −143.94 (ddd, J = 19.7, 10.7, 8.8 Hz, 2F). LRMS (LIFDI): m/z
was dissolved in pyridine-d to obtain the title compound. H NMR
5
+
72.00 (100%, [M] ). Anal. Calcd for C H F N O Pd ·0.1AgCl: C,
(500 MHz, CDCl ): δ 6.93 (dd, J = 9.6, 2.5 Hz, 1H), 6.78 (t, J = 7.8
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2
4
2
3
1
9
8.54; H, 3.82; N, 4.09. Found: C, 38.56; H, 3.85; N, 3.92.
Di-μ-acetatobis[o-dimethylaminomethyl-3,5-o,m-difluorophen-
Hz, 1H), 6.27−6.17 (m, 1H), 3.91 (s, 2H), 2.94 (s, 6H). F NMR
(471 MHz, CDCl ): δ −119.35 to −119.46 (dd, J = 16.4, 10.3 Hz).
3
yl-C,N)dipalladium(II) (2f). Complex 2f was prepared according to
general procedure A, on a 0.26 mmol scale, to afford the product as a
Di-μ-chlorobis[o-dimethylaminomethyl-2,4-o,m-difluorophenyl-
C,N)dipalladium(II) (3d). Complex 3d was obtained according to
general procedure B, with a reaction time of 1 week, on a 0.1 mmol
scale, to afford the product in a mixture of geometrical isomers (syn
and anti) as a yellow product (21 mg, 67%). Mp: 172.9−174.0 °C
1
yellow powder (71 mg, 82%). Mp: 205−208 °C (dec). H NMR (400
MHz, CDCl ): δ 6.54 (dd, J = 8.4 Hz, 2.4, 2H, H-2), 6.37−6.31 (m,
3
2
H, H-4), 3.56−3.46 (m, 4H, CHH′, CHH′), 2.80 (s, 6H, NCH ),
3
I
Organometallics XXXX, XXX, XXX−XXX