J. Yang et al. / Journal of Organometallic Chemistry 766 (2014) 73e78
77
[PdCl2(SIMes)]2(
The procedure yielded 122 mg (90%) of the pure product 1 as a
yellow powder. 1H NMR (400 MHz, CDCl3):
m
-dppe) (1)
[PdCl2(SIMes)]2(
The procedure yielded 123 mg (86%) of the pure product 5 as a
yellow powder. 1H NMR (400 MHz, CDCl3):
m-dpph) (5)
d
¼ 7.17e7.13 (m, 16H),
d
¼ 7.33e7.28 (m, 12H),
6.91 (s, 8H), 3.95 (s, 8H, NCH2CH2N), 2.47 (s, 24H, o-CH3), 2.25 (s,
7.22e7.19 (m, 8H), 7.00 (s, 8H), 4.00 (s, 8H, NCH2CH2N), 2.53 (s, 24H,
o-CH3), 2.38 (s, 12H, p-CH3), 1.99 (br, 4H, PCH2CH2CH2), 1.18 (br, 4H,
12H, p-CH3), 2.17 (br, 4H, PCH2). 13Ce{1H} NMR (100 MHz, CDCl3):
2
d
¼ 198.3 (d, JC,P ¼ 185.5 Hz, Ccarbene), 137.6 (o-CH3-C Ar), 137.1
PCH2CH2CH2), 1.08 (br, 4H, PCH2CH2CH2). 13Ce{1H} NMR (100 MHz,
(NeC Ar), 135.3 (p-CH3-C Ar), 133.6 (d, 3JC,P ¼ 10.6 Hz, CH Ph), 130.3
CDCl3):
d
¼ 198.2 (d, JC,P ¼ 184.4 Hz, Ccarbene), 137.7 (o-CH3-C Ar),
2
1
(d, JC,P ¼ 42.1 Hz, C Ph), 129.4 (CH Ph), 129.1 (CH Ph), 127.5 (d,
137.2 (NeC Ar), 135.3 (p-CH3-C Ar), 133.5 (d, 2JC,P ¼ 10.1 Hz, CH Ph),
4JC,P ¼ 10.0 Hz, CH Ph), 51.1 (d, JC,P ¼ 5.8 Hz, NCH2CH2N), 21.0 (p-
130.9 (d, 1JC,P ¼ 41.8 Hz, C Ph), 129.5 (d, 4JC,P ¼ 1.9 Hz, CH Ph), 129.0
4
CH3), 19.1 (o-CH3), 18.3 (PCH2). 31Pe{1H} NMR (121.5 MHz, CDCl3):
(CH Ph), 127.6 (d, JC,P ¼ 9.8 Hz, CH Ph), 51.1 (d, JC,P ¼ 6.2 Hz,
NCH2CH2N), 31.9 (PCH2CH2CH2), 22.6 (PCH2CH2CH2), 21.0 (p-CH3),
19.1 (o-CH3), 14.1 (PCH2CH2CH2). 31Pe{1H} NMR (121.5 MHz,
4
4
d
¼ 13.7. IR (KBr, cmꢀ1): 3441, 2961, 2918, 1488, 1454, 1435, 1300,
1267, 1178, 1103, 1028, 849, 721. Anal. Calc. for [PdCl2(SIMes)]2(m-
dppe) (C68H76Cl4N4P2Pd2): C, 59.79; H, 5.61; N, 4.10%. Found: C,
59.82; H, 5.31; N, 4.15%.
CDCl3):
d
¼ 11.9. IR (KBr, cmꢀ1): 3442, 2919, 2856, 1488, 1452, 1435,
1294, 1267, 1180, 1102, 1027, 912, 851, 739. Anal. Calc. for
[PdCl2(SIMes)]2(m-dpph) (C72H84Cl4N4P2Pd2): C, 60.81; H, 5.95; N,
3.94%. Found: C, 60.63; H, 5.77; N, 4.02%.
[PdCl2(SIPr)]2(
The procedure yielded 139 mg (91%) of the pure product 2 as a
yellow powder. 1H NMR (400 MHz, CDCl3):
m-dppe) (2)
[PdCl2(SIPr)]2(
The procedure yielded 132 mg (83%) of the pure product 6 as a
yellow powder. 1H NMR (400 MHz, CDCl3):
m-dpph) (6)
d
¼ 7.33e7.29 (m, 4H),
7.25e7.24 (m, 4H), 7.18e7.12 (m, 24H), 4.01 (s, 8H, NCH2CH2N), 3.46
(sept, J ¼ 6.8 Hz, 8H, CH(CH3)2), 1.92 (br, 4H, PCH2), 1.24 (d, J ¼ 6.4
Hz, 24H, CH(CH3)2), 1.17 (d, J ¼ 6.8 Hz, 24H, CH(CH3)2). 13Ce{1H}
d
¼ 7.44e7.41 (m, 4H),
7.28e7.23 (m, 20H), 7.17e7.14 (m, 8H), 4.08 (s, 8H, NCH2CH2N), 3.55
(sept, J ¼ 6.4 Hz, 8H, CH(CH3)2), 1.91 (br, 4H, PCH2CH2CH2), 1.33 (d,
J ¼ 6.4 Hz, 24H, CH(CH3)2), 1.23 (d, J ¼ 6.8 Hz, 24H, CH(CH3)2), 0.90
NMR (100 MHz, CDCl3):
d
¼ 200.0 (d, 2JC,P ¼ 184.2 Hz, Ccarbene), 147.7
(o-CH3-C Ar), 135.5 (NeC Ar), 133.9 (d, 4JC,P ¼ 10.5 Hz, p-CH3-C Ar),
130.1 (d, 1JC,P ¼ 42.2 Hz, C Ph), 129.3 (CH Ph), 128.7 (CH Ph), 127.4 (d,
(br, 8H, PCH2CH2CH2). 13Ce{1H} NMR (100 MHz, CDCl3):
d
¼ 200.0
2
4JC,P ¼ 9.8 Hz, CH Ph), 123.8 (CH Ph), 53.5 (d, JC,P ¼ 6.1 Hz,
4
(d, JC,P ¼ 183.3 Hz, Ccarbene), 147.7 (o-CH3-C Ar), 135.5 (NeC Ar),
133.5 (d, 2JC,P ¼ 9.9 Hz, CH Ph), 130.8 (d, 1JC,P ¼ 41.8 Hz, C Ph), 129.3
(d, 4JC,P ¼ 2.1 Hz, CH Ph), 128.8 (CH Ph), 127.4 (d, 4JC,P ¼ 9.7 Hz, CH
NCH2CH2N), 28.5 (CH(CH3)2), 26.8 (CH(CH3)2), 23.7 (CH(CH3)2), 19.0
(PCH2). 31Pe{1H} NMR (121.5 MHz, CDCl3):
d
¼ 15.7. IR (KBr, cmꢀ1):
4
Ph), 123.9 (CH Ph), 53.6 (d, JC,P ¼ 6.6 Hz, NCH2CH2N), 31.5
3051, 2962, 2867, 1477, 1447, 1435, 1327, 1269, 1243, 1106, 802, 755,
(PCH2CH2CH2), 28.5 (CH(CH3)2), 26.8 (CH(CH3)2), 23.6 (CH(CH3)2),
22.6 (PCH2CH2CH2), 14.1 (PCH2CH2CH2). 31Pe{1H} NMR (121.5 MHz,
715. Anal. Calc. for [PdCl2(SIPr)]2(
m-dppe) (C80H100Cl4N4P2Pd2): C,
62.63; H, 6.57; N, 3.65%. Found: C, 62.49; H, 6.31; N, 3.43%.
CDCl3):
d
¼ 11.9. IR (KBr, cmꢀ1): 3057, 2960, 2927, 1477, 1453, 1435,
1383, 1327, 1268, 1243, 1179, 1102, 1056, 929, 802, 756, 738. Anal.
[PdCl2(SIMes)]2(
The procedure yielded 121 mg (87%) of the pure product 3 as a
yellow powder. 1H NMR (400 MHz, CDCl3):
m-dppb) (3)
Calc. for [PdCl2(SIPr)]2(m-dpph) (C84H108Cl4N4P2Pd2): C, 63.44; H,
6.84; N, 3.52%. Found: C, 63.64; H, 6.52; N, 3.43%.
d
¼ 7.33e7.25 (m, 12H),
7.21e7.18 (m, 8H), 6.96 (s, 8H), 3.98 (s, 8H, NCH2CH2N), 2.51 (s, 24H,
o-CH3), 2.32 (s, 12H, p-CH3), 1.88 (br, 4H, PCH2CH2), 1.17 (br, 4H,
General procedure for the NHCePd catalysed BuchwaldeHartwig
amination
PCH2CH2). 13Ce{1H} NMR (100 MHz, CDCl3):
d
¼
198.2 (d,
2JC,P ¼ 184.2 Hz, Ccarbene), 137.7 (o-CH3-C Ar), 137.2 (NeC Ar), 135.3
The aryl chloride (0.50 mmol), amine (0.60 mmol), KOtBu
(0.75 mmol), NHCePd complex (0.0025 mmol) and dry dioxane
(1.0 mL) were added into oven-dried microwave vial. The reaction
mixture was irradiated in a microwave apparatus at 110 ꢁC for
10 min. After the reaction mixture was cooled to room temperature,
the product was filtered over Celite and washed with ethyl acetate.
Then the filtrate was concentrated with a rotary evaporator, and the
residue was then subjected to purification via flash column chro-
matography (eluent: ethyl acetate/petroleum ether) to give the
corresponding pure products.
2
(p-CH3-C Ar), 133.5 (d, JC,P
¼
10.3 Hz, CH Ph), 130.7 (d,
1JC,P ¼ 41.9 Hz, C Ph), 129.5 (d, 3JC,P ¼ 2.4 Hz, CH Ph), 129.0 (CH Ph),
4
4
127.6 (d, JC,P ¼ 9.9 Hz, CH Ph), 51.0 (d, JC,P ¼ 6.6 Hz, NCH2CH2N),
29.0 (PCH2CH2), 21.0 (p-CH3),19.1 (o-CH3), 18.4 (PCH2CH2). 31Pe{1H}
NMR (121.5 MHz, CDCl3):
d
¼ 13.6. IR (KBr, cmꢀ1): 3051, 2918, 1488,
1452, 1435, 1298, 1267, 1182, 1102, 851, 740. Anal. Calc. for
[PdCl2(SIMes)]2(m-dppb) (C70H80Cl4N4P2Pd2): C, 61.52; H, 6.20; N,
3.83%. Found: C, 61.74; H, 6.48; N, 4.04%.
[PdCl2(SIPr)]2(
The procedure yielded 127 mg (81%) of the pure product 4 as a
yellow powder. 1H NMR (400 MHz, CDCl3):
m-dppb) (4)
X-ray crystallography
d
¼ 7.39e7.24 (m, 10H),
7.22e7.15 (m, 22H), 4.05 (s, 8H, NCH2CH2N), 3.51 (sept, J ¼ 6.8 Hz,
8H, CH(CH3)2), 1.88 (br, 4H, PCH2CH2), 1.31 (d, J ¼ 6.8 Hz, 24H,
CH(CH3)2), 1.20 (d, J ¼ 6.8 Hz, 24H, CH(CH3)2), 0.91 (br, 4H,
Data collection was performed on a Bruker-AXS SMART CCD
area detector diffractometer at 296 K using
u rotation scans with a
¼ 0.71073 Å). Multi-scan
scan width of 0.3ꢁ and Mo-K
a
radiation (
l
PCH2CH2). 13Ce{1H} NMR (100 MHz, CDCl3):
d
¼
200.1 (d,
corrections were applied using SADABS [25]. Structure solutions
and refinements were performed with the SHELX-97 package [26].
All non-hydrogen atoms were refined anisotropically by full-matrix
least-squares on F2. The hydrogen atoms to carbon were included in
idealized geometric positions with thermal parameters equivalent
to 1.2 times those of carbon atoms. Complex 2 crystallized in poor
quality. The weak reflections cause a low observed/unique reflec-
tion ratio, which results in low completeness of the data set (0.918),
and gives insufficient strong reflections to support full refinement
of all non-hydrogen atoms. In complex 4, the crystal lattice contains
solvent accessible voids of 272 Å3, however, the final difference
2JC,P ¼ 183.6 Hz, Ccarbene), 147.7 (o-CH3-C Ar), 135.5 (NeC Ar), 133.5
2
(d, JC,P ¼ 10.0 Hz, CH Ph), 130.8 (d, 1JC,P ¼ 41.8 Hz, C Ph), 129.3 (d,
3JC,P ¼ 2.2 Hz, CH Ph), 128.8 (CH Ph), 127.6 (d, 4JC,P ¼ 9.8 Hz, CH Ph),
4
123.9 (CH Ph), 53.5 (d, JC,P ¼ 6.4 Hz, NCH2CH2N), 31.5 (PCH2CH2),
28.5 (CH(CH3)2), 26.8 (CH(CH3)2), 23.6 (CH(CH3)2), 22.6 (PCH2CH2).
31Pe{1H} NMR (121.5 MHz, CDCl3):
2925, 2864, 1476, 1453, 1436, 1382, 1324, 1269, 1244, 1180, 1100,
d
¼ 12.2. IR (KBr, cmꢀ1): 2962,
1058, 942, 800, 755, 736. Anal. Calc. for [PdCl2(SIPr)]2(m-dppb)
(C82H104Cl4N4P2Pd2): C, 61.75; H, 6.27; N, 3.79%. Found: C, 61.79; H,
6.41; N, 3.63%.