(d, 3JPC = 6.8 Hz, C7), 123.1 (s), 123.6 (s), 124.9 (s), 127.4 (d, JPC
=
2JAB = 8.3 Hz, 2H, OCH2), 7.19–7.31 (complex m, 2H, aromatic),
7.37–7.41 (m, 1H, aromatic), 7.52–7.55 (m, 1H, aromatic), 7.66–
7.72 (m, 1H, aromatic), 7.96–8.06 (complex m, 3H, aromatic).
13.6 Hz), 129.3 (s), 131.2 (d, JPC = 49.0 Hz), 131.4 (s), 132.0 (d,
JPC = 2.5 Hz), 132.9 (d, JPC = 12.4 Hz), 149.4 (d, 2JPC = 8.1 Hz,
1
1
C12), 167.2 (d, 3JPC = 1.3 Hz, C N). 31P{ H} NMR (121.5 MHz,
31P{ H} NMR (121.49 MHz, CDCl3, room temp.): d 124.8 (s).
=
CDCl3, room temp.): d 123.1 (s). Anal. Calcd for C20H22NO3P: C,
Anal. Calcd for C21H25ClNO3PPd: C, 49.24; H, 4.92; N, 2.73.
Found: C, 49.06; H, 4.99; N, 2.36%.
67.60; H, 6.24; N, 3.94. Found: C, 67.35; H, 6.41; N, 3.54%.
9a. Complex 9a was obtained using a similar procedure
to that described above for 3a, from 8a (0.89 g, 2.7 mmol)
and [PdCl2(COD)] (0.68 g, 0.88 equiv.). It was obtained as
a yellow solid (0.81 g, 68%). IR (KBr): 1653 (s, mC=N) cm−1.
1H NMR (500.13 MHz, DMSO, room temp.): d 1.71 [s, 3H,
NC(CH3)(CH3)], 1.75 [s, 3H, NC(CH3)(CH3)], AB spin system
(A = B = H, dA 4.40, dB 4.49, 2JAB = 8.6 Hz, 2H, COCH2), ABX
spin system (A = B = H, X = P, dA 4.88, dB 5.16, 2JAB = 14.2 Hz,
3JAX = 28.5 Hz, 3JBX = 14.1 Hz, 2H, POCH2), 7.37–7.42 (m, 2H,
aromatic), 7.50–7.55 (m, 1H, aromatic), 7.72–7.77 (complex m,
1H, aromatic), 7.87–7.91 (m, 1H, aromatic), 8.10–8.16 (m, 1H,
11a. Complex 11a was obtained using a similar procedure
to that described above for 5a, from 10a (0.427 g, 0.88 mmol)
and AgSO3CF3 (0.27 g, 1.2 equiv.). It was obtained as a yellow
1
solid (0.40 g, 76%). IR (KBr): 1653 cm−1 (m, mC=N). H NMR
(300.13 MHz, CDCl3, room temp.): d 1.00 (s, 3H, PdCH3), 1.61
[s, 3H, NC(CH3)(CH3)], 1.62 [s, 3H, NC(CH3)(CH3)], AB spin
system (A = B = H, dA 4.17, dB 4.23, 2JAB = 8.5 Hz, 2H, COCH2),
2
ABX spin system (A = B = H, X = P, dA 4.33, dB 4.67, JAB
=
14.9 Hz, 3JAX = 27.5 Hz, 3JBX = 12.4 Hz, 2H, POCH2), 7.27–7.36
(complex m, 2H, aromatic), 7.41–7.48 (m, 1H, aromatic), 7.58–
7.65 (complex m, 1H, aromatic), 7.74–7.80 (m, 1H, aromatic),
aromatic), 8.26–8.34 (complex m, 2H, aromatic). 31P{ H} NMR
7.99–8.09 (m, 3H, aromatic). 31P{ H} NMR (121.49 MHz, CDCl3,
1
1
1
(121.49 MHz, DMSO, room temp.): d 107.4 (s). Anal. Calcd for
C18H18Cl2NO3PPd: C, 42.84; H, 3.60; N, 2.78. Found: C, 42.68; H,
3.68; N, 2.51%.
room temp.): d 134.9 (s). 19F{ H} NMR (282.38 MHz, CDCl3): d
−78.1 (s). Anal. Calcd for C20H21F3NO6PPdS: C, 40.18; H, 3.54;
N, 2.34. Found: C, 39.84; H, 3.23; N, 2.37%.
9b. Complex 9b was obtained using a similar procedure to
that described above for 3a, from 8b (1.68 g, 4.7 mmol) and
[PdCl2(COD)] (1.19 g, 0.88 equiv.). It was obtained as a yellow
solid (1.46 g, 66%). IR (KBr): 1619 (s, mC=N) cm−1. 1H NMR
(300.13 MHz, DMSO, room temp.): d 1.59 [s, 3H, OC(CH3)(CH3)],
1.69 [s, 3H, NC(CH3)(CH3)], 1.80 [s, 3H, NC(CH3)(CH3)], 2.13 [s,
3H, OC(CH3)(CH3)], AB spin system (A = B = H, dA 4.49, dB 4.57,
2JAB = 8.5 Hz, 2H, OCH2), 7.37–7.44 (m, 2H, aromatic), 7.51–7.58
(m, 1H, aromatic), 7.74–7.78 (complex m, 1H, aromatic), 7.87–
7.93 (m, 1H, aromatic), 7.99–8.09 (m, 1H, aromatic), 8.26–8.35
11b. Complex 14b was obtained using a similar procedure
to that described above for 5a, from 10b (1.94 g, 3.79 mmol)
and AgSO3CF3 (1.17 g, 1.2 equiv.). It was obtained as a yellow
solid (2.01 g, 85%). IR (KBr): 1632 (s, mC=N) cm−1. 1H NMR
(300.13 MHz, CDCl3, room temp.): d 0.97 (s, 3H, PdCH3), 1.34 [d,
4JHP = 1.1 Hz, 3H, OC(CH3)(CH3)], 1.58 [s, 3H, NC(CH3)(CH3)],
1.66 [s, 3H, NC(CH3)(CH3)], 2.02 [s, 3H, OC(CH3)(CH3)], AB
2
spin system (A = B = H, dA 4.12, dB 4.22, JAB = 8.5 Hz, 2H,
OCH2), 7.19–7.24 (m, 1H, aromatic), 7.29–7.36 (m, 1H, aromatic),
7.40–7.47 (m, 1H, aromatic), 7.55–7.63 (m, 1H, aromatic), 7.70–
7.78 (m, 1H, aromatic), 7.92–8.03 (complex m, 3H, aromatic).
1
(complex m, 2H, aromatic). 31P{ H} NMR (121.49 MHz, DMSO,
1
room temp.): d 99.5 (s). Anal. Calcd for C20H22Cl2NO3PPd: C,
45.09; H, 4.16; N, 2.63. Found: C, 44.90; H, 4.33; N, 2.41%.
31P{ H} NMR (121.49 MHz, CDCl3, room temp.): d 125.6 (s).
1
19F{ H} NMR (282.38 MHz, CDCl3): d −78.1 (s). Anal. Calcd for
C22H25F3NO6PPdS: C, 42.22; H, 4.03; N, 2.24. Found: C, 42.09;
H, 3.87; N, 2.21%.
10a. Complex 10a was obtained using a similar procedure
to that described above for 3a, from 8a (1.03 g, 3.2 mmol) and
[PdClMe(COD)] (0.75 g, 0.8 equiv.). It was obtained as a pale
yellow solid (0.93 g, 68%). IR (KBr): 1654 (s, mC=N) cm−1. 1H
14a. A solution of 11a (0.17 g, 0.28 mmol) in CH2Cl2 (25 mL)
was stirred under 1 atm CO at room temperature for 3 h, the
CO was then replaced by 1 atm ethylene and the solution further
stirred for 1 h. Workup was as described for 7a, and afforded
14a as a yellow powder (0.17 g, 91% yield). IR (KBr): 1655 (m,
3
NMR (300.13 MHz, CDCl3, room temp.): d 0.92 (d, JHP
=
3.1 Hz, 3H, PdCH3), 1.77 [s, 3H, NC(CH3)(CH3)], 1.80 [s, 3H,
NC(CH3)(CH3)], AB spin system (A = B = H, dA 4.10, dB 4.19,
2JAB = 8.3 Hz, 2H, COCH2), ABX spin system (A = B = H, X =
P, dA 4.30, dB 4.67, 2JAB = 14.3 Hz, 3JAX = 27.6 Hz, 3JBX = 13.4 Hz,
2H, POCH2), 7.25–7.33 (complex m, 2H, aromatic), 7.39–7.45 (m,
1H, aromatic), 7.53–7.60 (complex m, 1H, aromatic), 7.70–7.77
1
mC=N), 1634 (m, mC=O) cm−1. H NMR (300.13 MHz, CDCl3): d
1.63 [s, 3H, NC(CH3)(CH3)], 1.64 [s, 3H, NC(CH3)(CH3)], broad
ABMNX system (A = B = M = N = H, X = P, dA 1.74, dB 1.93,
2H, PdCH2), 2.55 [s, 3H, C(O)CH3], broad ABMNX system (A =
(m, 1H, aromatic), 7.98–8.11 (complex m, 3H, aromatic). 31P{ H}
B = M = N = H, X = P, dA 3.15, dB 3.27, JAB = 20.6 Hz, 2H,
1
2
NMR (121.49 MHz, CDCl3, room temp.): d 134.2 (s). Anal. Calcd
for C19H21ClNO3PPd: C, 47.13; H, 4.37; N, 2.89. Found: C, 47.12;
H, 4.41; N, 2.64%.
PdCH2CH2), AB spin system (A = B = H, dA 4.30, dB 4.33, 2JAB
=
8.6 Hz, 2H, COCH2), ABX spin system (A = B = H, X = P, dA
4.44, dB 4.79, 2JAB = 15.5 Hz, 3JAX = 26.3 Hz, 3JBX = 12.5 Hz, 2H,
1
POCH2), 7.31–8.23 (complex m, 8H, aromatic). 31P{ H} NMR
10b. Complex 10b was obtained using a similar procedure
to that described above for 3a, from 8b (1.47 g, 4.1 mmol)
and [PdClMe(COD)] (0.98 g, 0.89 equiv.). It was obtained as a
yellow solid (1.21 g, 64%). IR (KBr): 1628 (s, mC=N) cm−1. 1H
1
(121.49 MHz, CDCl3): d 134.7 (s). 19F{ H} NMR (282.38 MHz,
CDCl3): d −78.6 (s). Anal. Calcd for C23H25F3NO7PPdS: C, 42.25;
H, 3.85; N, 2.14. Found: C, 41.95; H, 3.71; N, 2.00%.
3
NMR (300.13 MHz, CDCl3, room temp.): d 0.90 (d, JHP
=
14b. A solution of 11b (0.13 g, 0.21 mmol) in CH2Cl2 (25 mL)
was stirred under 1 atm CO at room temperature for 1 h, the CO
was then replaced by 1 atm ethylene and the solution further stirred
for 1 h. Workup was as described for 7a, and afforded 14b as a
2.6 Hz, 3H, PdCH3), 1.32 [s, 3H, OC(CH3)(CH3)], 1.77 [s,
3H, NC(CH3)(CH3)], 1.82 [s, 3H, NC(CH3)(CH3)], 2.05 [s, 3H,
OC(CH3)(CH3)], AB spin system (A = B = H, dA 4.03, dB 4.18,
768 | Dalton Trans., 2007, 759–770
This journal is
The Royal Society of Chemistry 2007
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