Organometallics
Article
13C{1H} NMR (100.8 MHz, DMSO-d6, 25 °C): δ 18.6 (Me), 19.3
C33H32Cl2N2O4.5PPd: C, 53.79; H, 4.38; N, 3.80. Found: C, 53.84; H,
4.32; N, 3.74.
(Me) 122.3 (C4), 124.5 (C7), 125.2 (C5), 125.4 (p-Xy), 127.7 (m-Xy),
128.4 (m-Xy), 129.7 (o-Xy), 130.2 (o-Xy), 130.3 (C6), 141.9 (ipso-Xy),
147.0 (C3), 147.1 (C2), 203.6 (C1). IR (Nujol, cm−1): ν(NH) 3187,
3162. Anal. Calcd for C30H30Cl2N4Pd2: C, 49.34; H, 4.14; N, 7.67.
Found: C, 48.90; H, 4.03; N, 7.48.
Crystals of SP-4-4-[PdCl{C,N-C(NHXy)C6H4NH2-2}-
PPh3]·0.5CH2Cl2·0.75Et2O suitable for an X-ray diffraction study
were obtained by slow diffusion of Et2O into a solution of the crude
reaction mixture in CH2Cl2. The crystals were dried in a vacuum oven
(70 °C, 14 h) and used to characterize the pure compound. Mp: 216
Synthesis of [Pd2(OAc)2{μ-N,C,N′-C(NXy)C6H4NH2-2}2]
(6b). To a suspension of 6a (110 mg, 0.15 mmol) in acetone (15
mL) was added TlTfO (110 mg, 0.31 mmol). The reaction mixture
was stirred for 1.5 h and then filtered through a short pad of Celite.
Then, to the filtered solution was added NaOAc (30 mg, 0.37 mmol)
and the reaction mixture was then stirred for 4 h. The resulting
suspension was filtered through a short pad of Celite. The resulting
solution was concentrated under vacuum (2 mL), and Et2O was added
(20 mL) to give a suspension, which was filtered. The collected solid
was washed first with Et2O (3 × 5 mL) and then dried first by suction
and then in an oven under vacuum (70 °C, 6 h) to give 6b as a pale
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°C dec. H NMR (400 MHz, CDCl3, 25 °C, TMS): δ 2.27 (s, 6 H,
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Me), 5.83 (s br, 2 H, NH2), 6.56 (dd, 1 H, JHH = 8.0 Hz, JHH = 0.4
Hz), 6.80 (br d, 1 H, 3JHH = 3.6 Hz), 6.97 (t, 1 H, 3JHH = 7.6 Hz), 7.22
3
(d, 2 H, JHH = 7.6 Hz, m-Xy), 7.34−7.48 (m, 3 H), 7.51−7.58 (m, 9
H, meta + p-PPh3), 7.72−7.77 (m, 6 H, o-PPh3), 11.61 (d br, 1 H, 4JHP
= 10.4 Hz, CNHXy). 13C{1H} NMR (100.8 MHz, CDCl3, 25 °C,
TMS): δ 18.3 (Me), 125.2 (CH), 126.1 (CH), 127.2 (CH), 128.3 (d,
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ipso-PPh3, JHH = 43.5 Hz), 128.5 (CH), 129.3 (CH), 129.5 (CH),
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129.6 (CH), 130.1 (CH), 131.5 (d, p-PPh3, JHH = 2.1 Hz), 134.2 (d,
o-PPh3, JHH = 11.8 Hz), 136.7 (C), 137.0 (CH), 137.13 (C3), 152.4
2
(C2), C1 not observed. 31P{1H} NMR (162.3 MHz, CDCl3, 25 °C): δ
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yellow solid. Yield: 111 mg, 0.14 mmol, 94%. Mp: 258 °C dec. H
36.8. IR (Nujol, cm−1): ν(NH) 3229, ν(PdCl) 323.
NMR (400 MHz, DMSO-d6, 25 °C): δ 1.29 (s, 3 H, Ac), 1.69 (s, 3 H,
3
MeXy), 2.61 (s, 3 H, MeXy), 5.98 (d, 1 H, JHH = 8 Hz), 6.73 (t, 1 H,
Synthesis of SP-4-3-[PdCl{C,N-C(NHXy)C6H4NH2-2}PPh3].
The NMR and IR data for this compound were obtained from the
crude reaction mixture. 1H NMR (400 MHz, CDCl3, 25 °C, TMS): δ
1.66 (s, 6 H, Me), 1.71 (br, 1 H, H2O), 6.30 (d, 1 H, 3JHH = 8.0 Hz),
6.85 (s br, 2 H, NH2, overlapped with resonances from the minor
3JHH = 8 Hz), 6.85 (d, 1 H, 3JHH = 8 Hz), 7.01−7.18 (m, 6 H), 7.25 (t,
3
2
1 H, JHH = 8 Hz), 8.74 (br d, 2 H, JHH = 10 Hz, N−H···OAc). IR
(Nujol, cm−1): ν(NH) 3252, 3489. Anal. Calcd for C34H36N4O4Pd2:
C, 52.52; H, 4.67; N, 7.21. Found: C, 52.21; H, 4.44; N, 6.89.
Synthesis of cis-[PdCl2{C,N-C(NXy)CMe2NHC6H4-2}L] (L =
XyNC (7a), PPh3 (7b)). To a suspension of 1 (for 7a, 77 mg, 0.19
mmol; for 7b, 70 mg, 0.17 mmol) in acetone (15 mL) was added the
appropriate ligand (for 7a, XyNC, 27.2 mg, 0.21 mmol; for 7b, PPh3,
50 mg, 0.19 mmol). After 2.5 (7a) or 4 h (7b) of stirring, the resulting
suspension was filtered and the solid collected was washed successively
with acetone (3 × 3 mL). 7b was additionally washed with CH2Cl2 (3
× 3 mL). The solid was dried by suction and, in the case of 7b, in a
vacuum oven (70 °C, 7 h).
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isomer), 6.93 (d, 2 H, JHH = 7.6 Hz, m-Xy), 7.14 (t, 1 H, JHH = 7.6
Hz, p-Xy), 7.33−7.49 (various m, 3 H, overlapped with resonances
from the minor isomer), 7.55 (m, 9 H, m- + p-PPh3, overlapped with
those from the minor isomer), 7.82 (dd, 6 H, 3JHH = 7.6 Hz, 3JHH = 4.4
Hz, o-PPh3), 8.69 (s br, 1 H, NH=C). 31P{1H} NMR (162.3 MHz,
CDCl3, 25 °C): δ 16.0. IR (Nujol, cm−1): ν(NH) 3229, ν(PdCl) 256.
Synthesis of SP-4-4- + SP-4-3-[PdCl{C,N-C(NHXy)C6H4NH2-
2}(PPh3)](TfO) (5′). To a suspension of 2c (80 mg, 0.12 mmol) in
CH2Cl2 (10 mL) was added TlTfO (40 mg, 0.11 mmol). The reaction
mixture was stirred for 30 min and then filtered through a short pad of
Celite. The solution was concentrated under vacuum (1 mL), and cold
Et2O was added (20 mL, 0 °C). The resulting suspension was stirred
for 15 min at 0 °C and then filtered. The collected solid was washed
with Et2O (3 × 5 mL) and dried first by suction and then in an oven
under vacuum (70 °C) for 7 h to give 5′ as a yellow solid consisting of
a mixture of the SP-4-4 and SP-4-3 isomers in a 1.33:1 molar ratio.
Yield: 60 mg, 0.08 mmol, 64%. Mp: 183 °C dec. 1H NMR (400 MHz,
CDCl3, 25 °C, TMS): δ 1.66 (s, 6 H, Me, minor isomer), 2.25 (s, 6 H,
Me, major isomer), 6.20 (s br, 2 H, NH2, major isomer), 6.25 (d, 1 H,
Data for 7a are as follows. Deep yellow solid. Yield: 79 mg, 0.14
mmol, 72%. Mp: 206 °C dec. 1H NMR (400 MHz, DMSO-d6, 25 °C):
δ 1.34 (br s, 3 H, CMe2), 1.51 (br s, 3 H, CMe2), 1.82 (s, 3 H, Me,
Xyq), 1.96 (s, 6 H, Me, XyPd), 2.67 (s, 3 H, Me, Xyq), 6.92 (d, 1 H,
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3JHH = 8 Hz, H4), 7.02−7.08 (m, 2 H), 7.20 (d, 2 H, JHH = 8 Hz, m-
XyPd), 7.30−7.38 (m, 3 H), 7.52−7.56 (m, 1 H), 8.25 (s, 1 H, NH),
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8.70 ppm (d, 1 H, JHH = 7 Hz, H7). IR (Nujol, cm−1): ν(NH) 3259,
ν(CN) 2184. Anal. Calcd for C28H30Cl5N3Pd: C, 48.58; H, 4.37; N,
6.07. Found: C, 48.19; H, 4.39; N, 6.09. Crystals of 7a·CHCl3 suitable
for an X-ray diffraction study were obtained by slow evaporation of a
solution of the complex in CHCl3 and were also used to get the
elemental analyses, melting point, and IR spectrum.
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3JHH = 8.0 Hz, minor isomer), 6.55 (d, 1 H, JHH = 8.0 Hz, major
3
isomer), 6.80 (t, 1 H, JHH = 7.6 Hz, minor isomer) 6.92−6.97 (m, 2
H, 1H (major isomer) + 1H (minor isomer)), 7.08 (br s, 2 H, NH2,
Data for 7b·H2O·Me2CO are as follows. Yellow solid. Yield: 109
3
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minor isomer), 7.13 (t, 1 H, JHH = 7.2 Hz, major isomer), 7.21 (d, 2
mg, 0.14 mmol, 81%. Mp: 202 °C dec. H NMR (400 MHz, DMSO-
H, 3JHH = 7.2 Hz, m-Xy, major isomer), 7.33 (d, 2 H, 3JHH = 7.6 Hz, m-
Xy, minor isomer), 7.35−7.46 (m, 4 H, 2H (major isomer) + 2H
(minor isomer)), 7.55 (m, 18 H, m- + p-PPh3, major + minor
isomers), 7.69−7.66 (m, 6 H, o-PPh3, major isomer), 7.81 (dd, 6 H,
d6, 25 °C): δ 0.80 (s, 3 H, Me), 1.14 (br s, 3 H, MeXy), 1.49 (br s, 3 H,
MeXy), 2.07 (s, 6 H, Me, Me2CO), 2.86 (s, 3 H, Me), 3.35 (br s, 1 H,
H2O), 6.81−6.91 (m, 4 H), 7.11−7.48 (various m, 16 H), 8.00 (s, 1 H,
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NH), 8.94 (d, 1 H, JHH = 8.0 Hz). 31P{1H} NMR (162.3 MHz,
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3JHH = 7.6 Hz, JHH = 4.0 Hz, o-PPh3, minor isomer), 8.85 (s br, 1 H,
DMSO-d6, 25 °C): δ 22.3. IR (Nujol, cm−1): ν(NH) 3276. Anal. Calcd
for C39H42Cl2N2O1.5PPd: C, 60.75; H, 5.49; N, 3.63. Found: C, 60.77;
H, 5.76; N, 3.71.
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CNHXy, minor isomer), 11.60 (d br, 1 H, JHP = 11.0 Hz, C
NHXy, major isomer). 31P{1H} NMR (162.3 MHz, CDCl3, 25 °C): δ
16.2 (minor isomer), 36.2 (major isomer). Anal. Calcd for
C34H31ClF3N2O3PPdS: C, 52.52; H, 4.02; N, 3.60; S, 4.12. Found:
C, 52.56; H, 3.79; N, 3.50; S, 3.95. IR (Nujol, cm−1): ν(NH) 3312,
ν(PdCl) 333, 260.
Synthesis of cis-[PdCl2{C,N-C(NXy)CH(Me)NHC6H4-2}PPh3]
(8a). To a suspension of 1 (90 mg, 0.22 mmol) in CH2Cl2 (5 mL)
were successively added MeCHO (100 μL, 1.77 mmol) and PPh3 (70
mg, 0.27 mmol), and the reaction mixture was stirred for 12 h. The
resulting suspension was filtered, and the solid that was collected was
washed with CH2Cl2 (3 × 5 mL) and dried, first by suction and then
in a vacuum oven (70 °C, 7 h), to give 8a as a deep yellow solid
consisting of a mixture of two isomers in a 2.3:1 molar ratio. Yield: 138
mg, 0.16 mmol, 71%. Mp: 203 °C. 1H NMR (300 MHz, DMSO-d6, 25
°C): major isomer, δ 0.96 (s, 3 H, MeXy), 1.30 (d, 3 H, 3JHH = 6.0 Hz,
CHMe), 2.93 (s, 3 H, MeXy), 4.74 (dq, 1 H, 3JHH = 6.3 Hz, 4JHH = 1.5
Hz, CHMe), 6.77−6.92 (m obscured by the resonances of the minor
Synthesis of [Pd2Cl2{μ-N,C,N′-C(NXy)C6H4NH2-2}2] (6a). To
a suspension of 1 (115 mg, 0.29 mmol) in CHCl3 (10 mL) was added
NEt3 (80 μL, 0.57 mmol). The reaction mixture was stirred for 3 h and
then filtered. The solid collected was washed successively with CHCl3
(3 × 5 mL) and methanol (3 × 3 mL) and dried, first by suction and
then in an oven under vacuum (70 °C, 6 h), to give 6a as a yellow
solid. Yield: 97 mg, 0.13 mmol, 93%. Mp: 273 °C dec. 1H NMR (400
MHz, DMSO-d6, 25 °C): δ 1.73 (s, 3 H, Me), 2.51 (s, 3 H, Me), 5.79
(d, 1 H, 3JHH = 7.2 Hz), 6.63 (t, 1 H, 3JHH = 6.4 Hz), 6.73 (d, 1 H, 3JHH
= 6.8 Hz), 6.79 (d, 1 H, 2JHH = 10.8 Hz, NH), 6.94 (t, 1 H, 3JHH = 6.8
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isomer, 3 H), 6.98 (d, 2 H, JHH = 6.0 Hz, m-Xy), 7.01−7.61 (several
m obscured by the resonances of the minor isomer, 16 H), 7.83 (br d
3
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Hz), 7.01 (d, 1 H, JHH = 6.4 Hz), 7.13 (t, 1 H, JHH = 6.8 Hz), 7.19
overlapped with that corresponding to the minor isomer, 1 H, JHH
=
(d, 1 H, 3JHH = 7.2 Hz), 7.38 (br d, 1 H, JHH = 10.8 Hz, N−H···Cl).
4.5 Hz, NH), 9.02 (d, 1 H, 3JHH = 7.8 Hz); minor isomer, δ 1.03 (d, 3
2
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dx.doi.org/10.1021/om200986k | Organometallics 2012, 31, 2697−2708
Martinez-Martinez, Antonio-Jesus
