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D. Li et al. / Journal of Organometallic Chemistry 695 (2010) 2781e2788
4.2.3. The characterization of ligand HL4
CH2SiMe3) ppm. 13C {1H} NMR (100 MHz, C6D6, 25 ꢁC):
1C, NC), 148.22 (s, 1C, ipso-C6H3(CH(CH3)CH2Y)(CH(CH3)2)), 146.28
d 172.42 (s,
1H NMR (400 MHz, CDCl3, 25 ꢁC):
d
7.92 (m, 4H, o-PPh2), 7.52 (br,
2
6H, m,p-PPh2), 7.46 (br, 5H, o,m,p-C6H5), 7.05 (br, 2H, m-C6H3iPr2),
(d, JPeC
¼
6.1 Hz, 1C, ipso-C6H3(CH(CH3)2)2), 145.22 (d,
3
2
6.68 (t, JHeH ¼ 7.0 Hz, 1H, p-C6H3iPr2), 3.97 (d, JPeH ¼ 14 Hz, 2H,
PCH2), 2.31 (m, 2H, C6H3(CHMe2)2), 1.76 (s, 3H, NCCH3), 0.96 (br,
JPeC ¼ 7.3 Hz, 1C, ipso-PPh2), 142.59 (d, JPeC ¼ 9.1 Hz, 1C, ipso-PPh2),
139.66 (s, 2C, o-C6H3(CH(CH3)2)2), 139.03 (s, 1C, o-C6H3(CH(CH3)
CH2Y)(CH(CH3)2)), 138.10 (s, 1C, o-C6H3(CH(CH3)CH2Y)(CH(CH3)2)),
133.18 (br, 4C, o-PPh2), 131.85 (d, 2C, m-PPh2), 128.74 (overlap with
C6D6, 2C, m-PPh2), 124.92, 124.75, 124.54, 124.20 (q, 6C, m,p-Ar),
123.25 (s, 1C, p-PPh2), 122.75 (s, 1C, p-PPh2), 71.06 (s, 2C, THF),
12H, C6H3(CH3)2) ppm. 13C NMR (75 MHz, CDCl3, 25 ꢁC):
d 165.11 (d,
2JPeC ¼ 6.0 Hz, 1C, NC), 161.18 (s, 1C, ipso-C6H3iPr2), 147.43 (s, 1C, o-
C6H3iPr2), 145.42 (s, 1C, ipso-C6H5), 145.47 (s, 1C, ipso-PPh2), 136.27
(s, 1C, ipso-PPh2), 134.86 (s, 1C, o-C6H3iPr2), 131.81 (m, 5C, o,p-PPh2),
2
2
130.92 (d, JPeC ¼ 11.8 Hz, 4C, m-PPh2), 128.95 (s, 1C, p-C6H3iPr2),
54.90, 53.67 (d, JPeC ¼ 123.3 Hz, 1C, NC(Me)CHP), 49.58 (d,
128.51 (s, 2C, m-C6H3iPr2), 123.35 (s, 2C, o-C6H5), 123.11 (s, 2C, p-
C6H5), 116.87 (s, 1C, m-C6H5), 41.47 (d, JPeC ¼ 60.7 Hz, 1C, PCH2),
28.27 (s, 2C, C6H3(CHMe2)2), 27.68 (s, 1C, NCCH3), 24.51 (s, 2C,
C6H3(CH(CH3)2)2), 23.47 (s, 2C, C6H3(CH(CH3)2)2) ppm. 31P NMR
JYeC ¼ 39.2 Hz, 1C, C6H3(CH(CH3)CH2Y)(CH(CH3)2)), 36.47 (s, 1C,
C6H3(CH(CH3)CH2Y)(CH(CH3)2), 29.74 (d, JYeC
¼
42.1 Hz, 1C,
YCH2Si), 29.13 (s, 1C, C6H3(CH(CH3)2)2), 28.90 (s, 1C, C6H3(CH
(CH3)2)2), 28.05 (s, 1C, C6H3(CH(CH3)CH2Y)(CH(CH3)2), 27.87, 27.74
(d, 2C, C6H3(CH(CH3)CH2Y)(CH(CH3)2) and C6H3(CH(CH3)2)2), 25.81
(s, 1C, C6H3(CH(CH3)2)2), 25.63 (s, 2C, C6H3(CH(CH3)CH2Y)(CH
(CH3)2), 25.53 (s, 1C, NCCH3), 25.37 (s, 2C, THF), 24.03 (s, 1C,
C6H3(CH(CH3)2)2), 23.67 (s, 1C, C6H3(CH(CH3)2)2), 5.35 (s, 3C, Si
(400 MHz, C6D6, 25 ꢁC):
C33H37N2P (492.63): C, 80.46; H, 7.57; N, 5.69. Found: C, 80.86; H,
7.92; N, 5.41%.
d
2.51, ꢀ3.12 ppm. Anal. Calcd for
4.2.4. The characterization of ligand HL5
(CH3)3) ppm. 31P NMR (400 MHz, C6D6, 25 ꢁC):
d 8.80 ppm. Anal.
1H NMR (300 MHz, CDCl3, 25 ꢁC):
d
8.79 (s, 1H, NH), 7.93 (m, 4H,
Calcd for C47H66N2OPSiY (823.21): C, 68.59; H, 8.08; N, 3.40. Found:
C, 68.87; H, 8.21; N, 3.23%.
o-PPh2), 7.47 (m, 4H, m,p-C6H3iPr2, o-C6H4CF3), 7.19 (m, 2H, p-PPh2),
7.07 (m, 5H, m-PPh2, p-C6H4CF3), 6.88 (m, 1H, m-C6H4CF3), 4.49 (d,
3
2JPeH ¼ 21 Hz, 1H, PCH), 2.81 (m, JHeH ¼ 6.9 Hz, 2H, C6H3(CH
4.3.2. The characterization of complex 2 L2Y(CH2SiMe3)(THF)2
(CH3)2)2), 1.70 (s, 3H, NCCH3), 1.07 (d, 3JHeH ¼ 6.9 Hz, 6H, C6H3(CH
1H NMR (400 MHz, C6D6, 25 ꢁC):
d
8.45 (d, 3JHeH ¼ 6.8 Hz, 1H, o-
3
3
(CH3)2)2), 0.78 (d, JHeH ¼ 6.9 Hz, 6H, C6H3(CH(CH3)2)2) ppm. 13C
PC6H4Y), 8.11 (m, 2H, m-C6H3iPr2), 7.92 (dd, JYeH ¼ 8 Hz,
{1H} NMR (75 MHz, CDCl3, 25 ꢁC):
d
164.36 (d, JPeC ¼ 6.0 Hz, 1C,
3JHeH ¼ 10.8 Hz, 1H, o-YC6H4P), 7.69 (t, JHeH ¼ 6.8 Hz, 1H, m-
2
3
NC), 160.95 (s, 1C, ipso-C6H3iPr2), 151.57 (s, 1C, o-C6H3iPr2), 150.69
(s, 1C, ipso-C6H5), 146.27 (s, 1C, ipso-PPh2), 144.32 (s, 1C, ipso-PPh2),
135.25 (s, 1C, o-C6H3iPr2), 133.32 (s, 1C, ispo-CF3eC6H4), 132.85 (s,
1C, CF3), 131.01 (m, 4C, o-PPh2), 130.49 (m, 2C, p-PPh2), 127.87 (d,
2JPeC ¼ 11.5 Hz, 4C, m-PPh2), 124.48 (s, 1C, p-C6H3iPr2), 122.62 (s, 2C,
m-C6H3iPr2), 122.24 (s, 1C, o-NC6H4CF3), 119.13 (s, 1C, m-NC6H4CF3),
118.24 (s, 1C, o-NC6H4CF3), 112.59 (s, 1C, p-NC6H4CF3), 71.62 (d,
JPeC ¼ 108 Hz, 1C, PCH2), 27.81 (s, 2C, C6H3(CHMe2)2), 26.66 (s, 1C,
NCCH3), 23.13 (s, 2C, C6H3(CH(CH3)2)2), 21.59 (s, 2C, C6H3(CH
PC6H4Y), 7.56 (br, 1H, m-YC6H4P, 2H, o-PC6H5, 2H, m-C6H3Et2), 7.50
3
3
(d, JHeH ¼ 7.6 Hz, 1H, m-PC6H5), 7.41 (t, JHeH ¼ 7.6 Hz, 1H,
p-PC6H5), 7.32 (br, 1H, m-PC6H5, 1H, p-C6H3Et2), 7.27 (overlap with
C6D6, 1H, p-C6H3iPr2), 5.08 (d, 2JPeH ¼ 23.6 Hz, 1H, PCH), 4.24 (sept,
3JHeH ¼ 6.8 Hz, 1H, ArCHMe2), 4.05 (m, 1H, ArCH2Me), 3.87 (s, 8H,
THF), 3.70 (m, 1H, ArCH2Me), 3.50 (m, 1H, ArCH2Me), 2.83 (m, 1H,
3
ArCH2Me), 2.46 (sept, JHeH ¼ 6.8 Hz, 1H, ArCHMe2) 2.08 (s, 3H,
3
NCCH3), 1.98 (t, JHeH
¼
7.6 Hz, 3H, ArCH2CH3), 1.84 (d,
3JHeH ¼ 6.8 Hz, 3H, ArCH(CH3)2), 1.74 (d, JHeH ¼ 6.8 Hz, 3H, ArCH
(CH3)2), 1.70 (s, 8H, THF), 1.47 (t, 3JHeH ¼ 7.6 Hz, 3H, ArCH2CH3), 1.20
(d, 3JHeH ¼ 6.8 Hz, 3H, ArCH(CH3)2),1.08 (d, 3JHeH ¼ 6.8 Hz, 3H, ArCH
3
(CH3)2)2) ppm. 31P NMR (400 MHz, C6D6, 25 ꢁC):
d 24.50, 20.41 ppm.
Anal. Calcd for C34H36F3N2P (560.63): C, 72.84; H, 6.47; N, 5.00.
Found: C, 73.24; H, 6.89; N, 4.67%.
(CH3)2), 0.48 (s, 9H, Si(CH3)3), ꢀ0.38 (s, 2H, CH2SiMe3) ppm. 13C {1H}
2
NMR (100 MHz, C6D6, 25 ꢁC):
d
198.31 (q, JPeC ¼ 36.0 Hz,
4.3. Synthesis and characterization of complexes 1e5
JYeC ¼ 36.0 Hz, 1C, ipso-YC6H4P), 168.30 (s, 1C, NC), 148.44 (s, 1C,
3
ipso-C6H3iPr2), 147.43 (d, JPeC ¼ 9 Hz, 1C, ipso-C6H3Et2), 145.99 (s,
Complexes 1e5 were obtained by the same synthetic method.
The reaction procedure was representatively described for 1. To
a solution of Y(CH2SiMe3)3(THF)2 (0.54 g, 1.1 mmol) in hexane
ligand HL1 (0.49 g, 1 mmol) in THF was added at ambient temper-
ature. The light yellow mixture was stirred for 0.5 h. The solution
was concentrated under vacuum and then was kept several days
at ꢀ30 ꢁC. Complexes 1e5 were isolated as microcrystalline solids.
The yields of 1e5 were respectively 53.6%, 62.8%, 70.4%, 68.3% and
67.1%.
1C, o-C6H3iPr2), 144.51 (s, 1C, o-C6H3iPr2), 140.78 (d, JPeC ¼ 5.7 Hz,
1C, ipso-PC6H5), 140.06 (d, JPeC ¼ 5.0 Hz, 1C, ipso-PC6H4Y), 139.88 (s,
1C, o-C6H3Et2), 138.72 (s, 1C, o-C6H3Et2), 136.19 (d, 3JPeC ¼ 23.2 Hz,
1C, o-PC6H4Y), 133.45 (d, 2C, o-C6H3iPr2), 131.91 (s, 1C, o-YC6H4P),
128.25 (overlap with C6D6,1C, p-C6H3iPr2),127.89 (s,1C, m-PC6H4Y),
126.08 (s, 1C, p-PC6H5), 125.78, 125.64, 125.51, 125.47 (m, 2C, o-
PC6H5, 2C, m-C6H3Et2), 125.02 (s, 1C, m-YC6H4P), 124.48 (s, 1C, m-
PC6H5), 123.33 (br, 1C, m-PC6H5, 1C, p-C6H3Et2), 77.94 (d,
JPeC ¼ 107 Hz, 1C, CHP), 69.14 (s, 4C, THF), 32.38 (d, JYeC ¼ 36.0 Hz,
1C, YCH2Si), 29.03 (s, 1C, C6H3(CHMe2)2), 28.23 (s, 1C,
C6H3(CHMe2)2), 26.33 (br, 1C, C6H3(CH2Me)2), 25.96 (s, 2C, C6H3(CH
(CH3)2)2), 25.52 (br, 1C, C6H3(CH2Me)), 25.11 (s, 1C, C6H3(CH
(CH3)2)2), 24.89 (s, 1C, C6H3(CH(CH3)2)2), 24.66 (s, 1C, NCCH3), 16.02
(s, 1C, C6H3(CH2CH3)2), 14.49 (s, 1C, C6H3(CH2CH3)2), 4.70 (s, 3C,
4.3.1. The characterization of complex 1 L1Y(CH2SiMe3)(THF)
1H NMR (400 MHz, C6D6, 25 ꢁC):
d 7.83 (br, 2H, o-PPh2), 7.52 (br,
2H, o-PPh2 and 1H, p-PPh2), 7.28 (br, 2H, m-PPh2 and 1H, p-PPh2),
7.16 (br, 2H, m-PPh2), 7.07 (br, 6H, m,p-C6H3iPr2), 3.72 (s, 2H, THF),
3.53 (br, 1H, PCH and 1H, C6H3(CH(CH3)2)2), 3.48 (s, 4H, THF), 3.32
CH2Si(CH3)3) ppm. 31P NMR (400 MHz, C6D6, 25 ꢁC):
d 6.68 ppm.
3
(sept, JHeH ¼ 6.8 Hz, 1H, C6H3(CH(CH3)2)2), 3.12 (br, 2H, C6H3(CH
Anal. Calcd for C49H70N2O2PSiY (866.42): C, 67.88; H, 8.14; N, 3.23.
Found: C, 68.21; H, 8.32; N, 3.01%.
(CH3)CH2Y)(CH(CH3)2)), 2.01 (s, 6H, C6H3(CH(CH3)CH2Y)(CH(CH3)2)
3
and NCCH3), 1.37 (d, JHeH ¼ 6.4 Hz, 3H, C6H3(CH(CH3)CH2Y)(CH
(CH3)2)), 1.20 (br, 3H, C6H3(CH(CH3)2)2 and 4H, THF), 1.14 (d,
4.3.3. The characterization of complex 3 L3Y(CH2SiMe3)(THF)2
3JHeH
¼
6.8 Hz, C6H3(CH(CH3)CH2Y)(CH(CH3)2)), 1.00 (d,
1H NMR (400 MHz, C6D6, 25 ꢁC):
d 7.75 (m, 2H, o-PPh2), 7.54 (m,
3
3JHeH ¼ 6.8 Hz, 3H, C6H3(CH(CH3)2)2), 0.69 (d, JHeH ¼ 6.8 Hz, 3H,
2H, o-PPh2), 7.49 (s, 1H, m-C6H3iPr2), 7.28 (overlap with C6D6, 2H,
m,p-C6H3iPr2), 7.21 (br, 2H, m-C6H3(CH2Y)Me), 7.12 (br, 4H,
m,p-PPh2 and p-C6H3(CH2Y)Me), 7.05 (br, 3H, m,p-PPh2), 3.72 (d,
2JPeH ¼ 16.0 Hz, 1H, PCH), 3.64 (br, 8H, THF), 3.12 (m, 1H, CHMe2),
C6H3(CH(CH3)2)2), 0.63 (s, 9H, Si(CH3)3), 0.48 (d, 3JHeH ¼ 6.8 Hz, 3H,
2
C6H3(CH(CH3)2)2), 0.57, 0.02 (ABX, JHeH ¼ 11.0 Hz, 2H, C6H3(CH
2
(CH3)CH2Y)(CH(CH3)2)), 0.16, ꢀ0.20 (ABX, JHeH ¼ 10.4 Hz, 2H,