Aminopyrimidinyl Phosphanes Undergoing C–H Activation
H, 4-H), 7.61 (m, 5-H), 8.31 (d, 1 H, 9-H) ppm. 13C NMR ([D6]-
DMSO, 100.61 MHz): δ = 36.3 [s, N(CH3)2], 108.4 (s, C-8), 128.4,
128.4 (2ϫ s, C-m, C-p), 129.1 (d, 3JCP = 12.8 Hz, C-2), 129.3, 129.3
Experimental Section
General: Solvents were purified and dried by standard methods. All
reactions were carried out under an atmosphere of dinitrogen. The
ligand precursor 1 and the palladium(II) complex (C6H5CN)2PdCl2
were synthesised according to procedures published in the litera-
ture.[19,17b] The NMR spectra are assigned according to Scheme 4.
2
(2ϫ s, C-3, C-4), 133.2 (d, JCP = 19.4 Hz, 4 C, C-o), 134.7 (s, C-
1
1
5), 135.3 (d, JCP = 19.4 Hz, C-1), 138.2 (d, JCP = 12.9 Hz, C-i),
144.6 (d, 2JCP = 24.0 Hz, C-6), 157.8 (s, C-9), 161.1 (s, C-10), 166.4
(s, C-7) ppm. 31P NMR ([D6]DMSO, 161.98 MHz): δ = –12.04 (s)
ppm.
2d: From pyrrolidinylguanidinium sulfate, yield 3.12 g (91%).
C26H24N3P (409.47): calcd. C 76.27, H 5.91, N 10.26; found C
1
76.11, H 5.99, N 10.20. H NMR ([D6]DMSO, 400.13 MHz): δ =
1.55–1.80 [br., 4 H, N(CH2CH2)2], 2.81 [br., 2 H, N(CH2CH2)2],
3
3.36 [br., 2 H, N(CH2CH2)2], 6.73 (d, JHH = 5.1 Hz, 1 H, 8-H),
6.97 (m, 1 H, 2-H), 7.12–7.20 (m, 4 H, m-H), 7.30–7.36 (m, 6 H,
o-H, p-H), 7.39 (t, 3JHH = 7.4 Hz, 1 H, 3-H), 7.49 (t, 3JHH = 7.4 Hz,
1 H, 4-H), 7.63 (m, 1 H, 5-H), 8.31 (d, 1 H, 9-H) ppm. 13C NMR ([D6]-
DMSO, 100.61 MHz): δ = 24.8 [s, N(CH2CH2)2], 45.7 [br.,
N(CH2CH2)2], 108.3 (s, C-8), 128.3, 128.3 (2ϫ s, C-m, C-p), 129.0
Scheme 4. Numbering scheme for assignment of the NMR signals.
General Synthesis of Ligands 2a-e: 1 (3.0 g, 8.35 mmol) and the
appropriate substituted guanidinium sulfate (12 mmol) were sus-
pended in dry EtOH (40 mL). After the addition of KOH (0.67 g),
the mixture was heated under reflux for 20 h. After the removal of
the solvent in vacuo, the residue was dissolved in a mixture of water
and CH2Cl2. The layers were separated and the aqueous layer was
extracted with CH2Cl2 (10 mL). The combined organic layers were
dried with anhydrous magnesium sulfate, filtered and concentrated
in vacuo. The crude material was crystallised from ethanol to afford
the desired ligands 2a–e in yields of Ͼ90%.
3
(d, JCP = 13.9 Hz, C-2), 129.2, 129.2 (2ϫ s, C-3, C-4), 133.3 (d,
1
2JCP = 19.4 Hz, C-o), 134.8 (s, C-5), 135.3 (d, JCP = 20.3 Hz, C-
1
2
1), 138.4 (d, JCP = 13.0 Hz, C-i), 144.7 (d, JCP = 24.0 Hz, C-6),
3
157.8 (s, C-9), 159.3 (s, C-10), 166.3 (d, JCP = 1.9 Hz, C-7) ppm.
31P NMR ([D6]DMSO, 161.98 MHz): δ = –12.08 (s) ppm.
2e: From piperidinylguanidinium sulfate, yield 3.11 g (90%).
C27H26N3P (423.50): calcd. C 76.58, H 6.19, N 9.92; found C 76.53,
H 6.30, N 9.80. 1H NMR ([D6]DMSO, 400.13 MHz): δ = 1.26 [br.,
4 H, N(CH2CH2)2CH2], 1.47 [br., 2 H, N(CH2CH2)2CH2], 3.34 [br.,
3
2a: From guanidinium sulfate, yield 2.84 g (96%). C22H18N3P
4 H, N(CH2CH2)2CH2], 6.75 (d, JHH = 5.1 Hz, 1 H, 8-H), 6.99
(355.38): calcd. C 74.35, H 5.11, N 11.82; found C 74.01, H 5.25,
(m, 1 H, 2-H), 7.13–7.16 (m, 4 H, m-H), 7.20–7.35 (m, 6 H, o-H,
1
3
3
N 11.75. H NMR ([D6]DMSO, 400.13 MHz): δ = 6.25 (br., 2 H,
p-H), 7.39 (t, JHH = 7.8 Hz, 1 H, 3-H), 7.49 (t, JHH = 7.4 Hz, 1
H, 4-H), 7.62 (m, 1 H, 5-H), 8.33 (d, 1 H, 9-H) ppm. 13C NMR
([D6]DMSO, 100.61 MHz): δ = 24.2 [s, N(CH2CH2)2CH2], 25.5 [s,
N(CH2CH2)2CH2], 43.9 [s, N(CH2CH2)2CH2], 108.5 (s, C-8), 128.4,
128.4 (2ϫ s, C-m, C-p), 129.2 (d, 3JCP = 17.5 Hz, C-2), 129.3, 129.4
NH2), 6.67 (d, 3JHH = 4.8 Hz, 1 H, 8-H), 6.98 (m, 1 H, 2-H), 7.12–
3
7.23 (m, 4 H, m-H), 7.30–7.36 (m, 6 H, o-H, p-H), 7.38 (t, JHH
=
3
7.8 Hz, 1 H, 3-H), 7.47 (t, JHH = 7.3 Hz, 1 H, 4-H), 7.63 (m, 1 H,
5-H), 8.16 (d,
1
H, 9-H) ppm. 13C NMR ([D6]DMSO,
4
2
100.61 MHz): δ = 109.7 (d, JCP = 4.6 Hz, C-8), 128.6 (s, C-m),
(2ϫ s, C-3, C-4), 133.2 (d, JCP = 19.4 Hz, C-o), 134.9 (s, C-2),
3
135.3 (d, 1JCP = 19.4 Hz, C-1), 138.4 (d, 1JCP = 12.9 Hz, C-i), 144.6
128.6 (s, C-p), 128.8 (d, JCP = 28.5 Hz, C-2), 129.2 (br., C-3, C-
2
1
2
4), 133.2 (d, JCP = 20.4 Hz, C-o), 134.3 (s, C-5), 135.4 (d, JCP
=
=
=
(d, JCP = 24.0 Hz, C-6), 158.0 (s, C-9), 160.3 (s, C-10), 166.5 (d,
1
2
3JCP = 1.9 Hz, C-7) ppm. 31P NMR ([D6]DMSO, 161.98 MHz): δ
20.4 Hz, C-1), 138.0 (d, JCP = 11.1 Hz, C-i), 143.6 (d, JCP
3
24.0 Hz, C-6), 157.8 (s, C-9), 162.6 (s, C-10), 165.8 (d, JCP
= –12.22 (s) ppm.
2.8 Hz, C-7) ppm. 31P NMR ([D6]DMSO, 161.98 MHz): δ = –12.05
General Synthesis of the Palladium Complexes: 3a,b and 4c–e were
obtained by treating (C6H5CN)2PdCl2 with ligands 2a–e in equi-
molar amounts according to the following general method: A solu-
tion of the appropriate ligand 2a–e (0.30 mmol) in CH2Cl2 (5 mL)
was added to a solution of [(C6H5CN)2PdCl2] (0.115 g, 0.30 mmol)
in CH2Cl2 (20 mL). The mixture was stirred for 16 h at room tem-
perature. Addition of diethyl ether (50 mL) caused precipitation of
the product, which was further washed two times with diethyl ether
(20 mL) and dried in the vacuum giving yields of 80–95%.
(s) ppm.
2b: From N-ethylguanidinium sulfate, yield 3.01 g (94%).
C24H22N3P (383.43): calcd. C 75.18, H 5.78, N 10.95; found C
74.61, H 5.82, N 10.80. H NMR ([D6]DMSO, 400.13 MHz): δ =
0.82 (br., 3 H, NCH2CH3), 2.75 (br., 2 H, NCH2CH3), signal not
observed: NH, δ = 6.68 (br., 1 H, 8-H), 6.98 (m, 1 H, 2-H), 7.12–
7.23 (m, 4 H, m-H), 7.30–7.36 (m, 6 H, o-H, p-H), 7.39 (t, JHH
1
3
=
3
7.8 Hz, 1 H, 3-H), 7.49 (t, JHH = 7.4 Hz, 1 H, 4-H), 7.61 (m, 1 H,
5-Hpyrim), 8.21 (d, 3JHH = 5.1 Hz, 1 H, 9-H) ppm. 13C NMR ([D6]-
3a: From 2a, yield 0.149 g (93%). C22H18Cl2N3PPd (532.68): calcd.
DMSO, 100.61 MHz):
δ = 14.8 (s, NCH2CH3), 34.92 (s,
1
C 49.60, H 3.41, N 7.89; found C 49.35, H 3.62, N 7.80. H NMR
NCH2CH3), 109.0 (s, C-8), 128.4 (s, C-m), 128.5 (s, C-p), 128.8 (d,
3
3JCP = 16.6 Hz, C-2), 129.2, 129.3 (2ϫ s, C-3, C-4), 133.2 (d, JCP
2
([D6]DMSO, 400.13 MHz): not det. NH2, δ = 6.89 (d, JHH
=
1
4.7 Hz, 1 H, 8-H), 7.18 (m, 2 H, 2-H), 7.23–7.68 (m, 10 H, o-H, m-
H, p-H), 7.78 (t, 3JHH = 7.8 Hz, 1 H, 3-H), 7.91 (t, 3JHH = 7.8 Hz, 1
H, 4-H), 8.09 (m, 1 H, 5-H), 8.23 (d, 1 H, 9-H) ppm. 31P NMR
([D6]DMSO, 161.98 MHz): δ = 31.27 (s) ppm.
= 20.3 Hz, C-o), 134.7 (s, C-5), 135.3 (d, JCP = 19.6 Hz, C-1),
138.2 (d, 1JCP = 12.0 Hz, C-i), 144.5 (br., C-6), 157.9 (s, C-9), 161.5
(s, C-10), 166.2 (s, C-7) ppm. 31P NMR ([D6]DMSO, 161.98 MHz):
δ = –12.05 (s) ppm.
2c: From N,N-dimethylguanidinium sulfate, yield 2.98 g (93%).
3b: From 2b, yield 0.151 g (90%). C24H22Cl2N3PPd (560.74): calcd.
1
C24H22N3P (383.43): calcd. C 75.18, H 5.78, N 10.95; found C
C 51.41, H 3.95, N 7.49; found C 51.07, H 3.93, N 7.33. H NMR
1
3
75.20, H 5.88, N 10.93. H NMR ([D6]DMSO, 400.13 MHz): δ = ([D6]DMSO, 400.13 MHz): δ = 1.13 (t, JHH = 7.0 Hz, 3 H,
3
3
2.80 [br., 6 H, N(CH3)2], 6.71 (d, JHH = 4.7 Hz, 1 H, 8-H), 6.98 NCH2CH3), 3.51 (br., 2 H, NCH2CH3), 6.87 (d, JHH = 5.1 Hz, 1
(m, 1 H, 2-H), 7.10–7.21 (m, 4 H, m-H), 7.22–7.35 (m, 6 H, o-H, H, 8-H), 7.19 (m, 1 H, 2-H), 7.25–7.72 (m, 10 H, o-H, m-H, p-H),
3
3
3
3
p-H), 7.38 (t, JHH = 7.8 Hz, 1 H, 3-H), 7.48 (t, JHH = 7.4 Hz, 1
7.78 (t, JHH = 7.8 Hz, 1 H, 3-H), 7.91 (t, JHH = 7.8 Hz, 1 H, 4-
Eur. J. Inorg. Chem. 2011, 4603–4609
© 2011 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim
www.eurjic.org
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