C.S. Lee et al. / Journal of Organometallic Chemistry 772-773 (2014) 172e181
179
compound was purified by recrystallizing in toluene at ꢁ35 ꢂC
Complex 17
(0.061 g, 51%). The compound was slowly decomposed in C6D6
during the overnight acquisition of the 13C NMR data. 1H NMR
The title complex was synthesized using the same conditions
and procedure as those for 15 using 10 (0.100 g, 0.287 mmol). It
was obtained as a yellow solid in 77% yield (0.155 g). 1H NMR
(C6D6):
d
7.37 (dd, J ¼ 8.0, 14 Hz, 4H), 7.20e7.04 (m, 13H), 7.01e6.95
(m, 2H), 6.92e6.82 (m, 7H), 6.65 (dd, J ¼ 5.2, 8.0 Hz, 1H), 6.47 (dd,
J ¼ 7.8, 14 Hz, 1H), 6.39 (dt, J ¼ 7.2, 3.6 Hz, 1H), 2.48 (s, 3H, CH3), 2.35
(C6D6):
d
7.37 (t, J ¼ 7.6 Hz, 2H), 7.21 (dt, J ¼ 8.2, 0.8 Hz, 2H), 6.89
(t, J ¼ 7.4 Hz, 2H), 6.85e6.78 (m, 3H), 6.70e6.53 (m, 9H),
6.47e6.36 (m, 4H), 6.09 (dt, J ¼ 7.4, 1.4 Hz, 1H), 3.94e3.82 (m, 2H,
NCH2), 3.50e3.48 (m, 2H, NCH2), 2.51 (s, 2H, HfCH2), 2.12 (s, 2H,
HfCH2), 1.12 (t, J ¼ 6.6 Hz, 3H, CH3) ppm. 13C{1H} NMR (C6D6):
(s, 6H, HfCH2) ppm. 31P{1H} NMR (C6D6):
d 37.31 ppm. Anal. Calcd
(C40H38NPSHf): C, 62.05; H, 4.95; N,1.81. Found: C, 61.94; H, 4.85; N,
1.95%.
d
161.19 (d, JPC ¼ 29 Hz), 146.02, 135.34 (d, JPC ¼ 2.3 Hz), 134.40 (d,
Complex 14
JPC ¼ 32 Hz), 133.20 (d, JPC ¼ 12 Hz), 132.69, 132.13 (d, JPC ¼ 12 Hz),
129.83, 128.56 (d, JPC ¼ 2.3 Hz), 127.99, 127.86, 127.01 (d,
JPC ¼ 3.8 Hz), 124.56, 120.92, 118.70, 118.29, 118.22, 112.28 (d,
JPC ¼ 9.1), 73.35 (d, JPC ¼ 8.3) 73.24, 36.90 (d, JPC ¼ 5.3 Hz),
The title complex was synthesized using the same conditions
and procedure as those for 11 using 7 (0.087 g, 0.25 mmol). The
compound was purified by recrystallizing in toluene at ꢁ35 ꢂC
(0.100 g, 51%). The compound was slowly decomposed in C6D6
during the overnight acquisition of the 13C NMR data. 1H NMR
13.34 ppm. 31P{1H} NMR (C6D6):
d 6.69 ppm. Anal. Calcd
(C36H37N2PHf): C, 61.14; H, 5.27; N, 3.96. Found: C, 60.94; H,
5.02; N, 4.21%.
(C6D6):
d
7.31 (dd, J ¼ 7.6, 13.6 Hz, 4H), 7.17 (t, J ¼ 7.6 Hz, 6H), 7.07 (d,
J ¼ 7.2 Hz, 6H), 6.90 (d, J ¼ 7.6 Hz, 2H), 6.84 (t, J ¼ 7.4 Hz, 4H), 6.79
(dt, J ¼ 7.4, 7.4 Hz, 4H), 6.58e6.46 (m, 2H), 6.33 (dt, J ¼ 7.6, 1.2 Hz,
1H), 3.26e3.17 (quartet, J ¼ 6.4 Hz, 2H, NCH2), 2.40 (s, 6H, HfCH2),
Complex 18
The title complex was synthesized using the same conditions
and procedure as those for 15 using 10 (0.100 g, 0.287 mmol) and
Zr(CH2Ph)4 instead of Hf(CH2Ph)4. It was obtained as a yellow solid
0.23 (t, J ¼ 6.6 Hz, 3H, CH3) ppm. 31P{1H} NMR (C6D6):
d 35.29 ppm.
Anal. Calcd (C41H40NPSHf): C, 62.47; H, 5.11; N, 1.78. Found: C,
62.25; H, 5.02; N, 1.89%.
in 71% yield (0.126 g). 1H NMR (C6D6):
d
7.43 (dt, J ¼ 7.7, 1.6 Hz, 2H),
7.18 (dt, J ¼ 5.4, 1.2 Hz, 2H), 6.91 (t, J ¼ 7.6 Hz, 2H), 6.85e6.78 (m,
3H), 6.70e6.57 (m, 7H), 6.47e6.35 (m, 6H), 5.95 (tt, J ¼ 7.0, 1.6 Hz,
1H), 4.07e3.94 (m, 2H, NCH2), 3.52e3.39 (m, 2H, NCH2), 2.84 (s, 2H,
HfCH2), 2.38 (s, 2H, HfCH2), 1.09 (t, J ¼ 6.6 Hz, 3H, CH3) ppm. 13C{1H}
Complex 15
Hf(CH2Ph)4 (0.132 g, 0.24 mmol) and 8 (0.098 g, 0.24 mmol)
were mixed in toluene (2 mL) at ꢁ30 ꢂC. The temperature was
raised slowly to room temperature, and the solution was stirred
overnight. After the solvent was removed under vacuum, the res-
idue was triturated in hexane (~0.5 mL). The yellow solid was iso-
NMR (C6D6):
d
159.91 (d, JPC ¼ 30 Hz), 147.31, 135.14, 132.90, 132.79
(d, JPC ¼ 26 Hz), 132.68, 132.19 (d, JPC ¼ 12 Hz), 130.75, 127.98,
126.42,125.89,124.13,120.28,119.84,119.46,118.56 (d, JPC ¼ 5.3 Hz),
111.83 (d, JPC ¼ 9.8 Hz), 64.61 (d, JPC ¼ 6.8), 64.49, 37.27 (d,
lated by decantation (0.128 g, 70%). 1H NMR (C6D6):
d 7.37 (t,
JPC ¼ 4.5 Hz), 13.35 ppm. 31P{1H} NMR (C6D6):
d
ꢁ0.08 ppm. Anal.
J ¼ 7.0 Hz, 2H), 7.25 (t, J ¼ 7.6 Hz, 2H), 7.10 (d, J ¼ 6.8 Hz, 2H), 7.01 (d,
J ¼ 7.6 Hz, 2H), 6.91 (t, J ¼ 6.8 Hz, 2H), 6.93e6.83 (m, 4H), 6.66e6.60
(m, 4H), 6.55 (t, J ¼ 7.6 Hz, 2H), 6.26 (t, J ¼ 7.4 Hz, 1H), 4.67e4.58 (m,
2H, 2-quinaldine), 2.83e2.72 (m, 2H, 4-quinaldine), 2.47e2.37 (m,
2H, 4-quinaldine), 2.41 (s, 2H, HfCH2), 1.93 (s, 2H, HfCH2), 1.87e1.75
(m, 2H, 3-quinaldine) 1.75e1.53 (m, 2H, 3-quinaldine) 1.10 (d,
Calcd (C36H37N2PZr): C, 69.75; H, 6.02; N, 4.52. Found: C, 69.44; H,
5.79; N, 4.72%.
Complex 19
J ¼ 6.4 Hz, CH3) ppm. 13C{1H} NMR (C6D6):
158.11 (d, JPC ¼ 31 Hz),
d
Hf(NMe2)4 (0.266 g, 0.75 mmol) and 8 (0.300 g, 0.75 mmol)
were mixed in toluene (5 mL) at room temperature, and the solu-
tion was stirred overnight at this temperature. After the solvent
was removed under vacuum, the residue was triturated in hexane
(~1 mL). After the resulting bis(dimethylamido)hafnium complex
(0.444 g, 0.668 mmol) was dissolved in toluene (15 mL), Me3SiCl
(0.725 g, 6.68 mmol) was added. The solution was stirred at room
temperature overnight. After the solvent was removed under vac-
uum, the residue was triturated in hexane (~1 mL). The yellow solid
was isolated by decantation (0.408 g). In the 1H NMR spectrum,
some impurity was detected (see SI), of which removal was un-
149.32, 135.67, 135.49, 135.18, 133.66 (d, JPC ¼ 2.3 Hz), 132.80, 131.75
(d, JPC
¼
12 Hz), 129.15, 127.29, 126.85, 123.65, 122.35 (d,
JPC ¼ 9.9 Hz), 121.45, 118.74 (d, JPC ¼ 6.1 Hz), 118.01, 117.59, 117.80 (d,
JPC ¼ 42 Hz), 78.18, 72.74 (d, JPC ¼ 11 Hz), 45.35 (d, JPC ¼ 5.3 Hz),
26.01, 22.34, 19.15 ppm. 31P{1H} NMR (C6D6):
d 5.42 ppm. Anal.
Calcd (C40H41N2PHf): C, 63.28; H, 5.44; N, 3.69. Found: C, 63.54; H,
5.61; N, 3.91%.
Complex 16
The title complex was synthesized using the same conditions
and procedure as those for 15 using 8 (0.050 g, 0.13 mmol) and
Zr(CH2Ph)4 instead of Hf(CH2Ph)4. It was obtained as a yellow solid
successful. 1H NMR (C6D6):
d 7.34e7.23 (m, 4H), 6.95e682 (m, 5H),
6.67 (dt, J ¼ 7.5, 1.5 Hz, 2H), 5.07e4.98 (m, 2H, 2-quinaldine),
2.66e2.53 (m, 2H, 4-quinaldine), 2.30e2.20 (m, 2H, 4-quinaldine),
1.95e1.83 (m, 2H, 3-quinaldine), 1.60e1.51 (m, 2H, 3-quinaldine),
1.22 (d, J ¼ 6.4 Hz, 6H, CH3) ppm.
in 85% yield (0.071 g). 1H NMR (C6D6):
d
7.41 (t, J ¼ 6.8 Hz, 2H), 7.27
(t, J ¼ 7.6 Hz, 2H), 7.15 (d, J ¼ 4.8 Hz, 2H), 6.97 (d, J ¼ 7.2 Hz, 3H),
6.91e6.86 (m, 3H), 6.83e6.76 (m, 2H), 6.64 (dt, J ¼ 7.4, 1.4 Hz, 2H),
6.55 (d, J ¼ 6.8 Hz, 2H), 6.47 (t, J ¼ 7.6 Hz, 2H), 6.06 (t, J ¼ 7.2 Hz,1H),
4.76e4.66 (m, 2H, 2-quinaldine), 2.82e2.68 (m, 2H, 4-quinaldine),
2.76 (s, 2H, HfCH2), 2.48e2.38 (m, 2H, 4-quinaldine), 2.27 (s, 2H,
HfCH2), 1.93e1.82 (m, 2H, 3-quinaldine), 1.60e1.50 (m, 2H, 3-
quinaldine), 1.05 (d, J ¼ 6.4 Hz, CH3) ppm. 13C{1H} NMR (C6D6):
Complex 20
The title complex was synthesized using the same conditions
and procedure as those for 19 using 8 (0.150 g, 0.375 mmol) and
Zr(NMe2)4 instead of Hf(NMe2)4. Orange solid was isolated
(0.190 g). In the 1H NMR spectrum, some impurity was detected
d
157.04 (d, JPC ¼ 32 Hz), 150.63, 133.82, 133.55 (d, JPC ¼ 2.2 Hz),
132.74 (d, JPC ¼ 2.2 Hz),132.17 (d, JPC ¼ 12 Hz),130.55,128.53,128.17,
126.73, 126.01, 124.12, 121.47 (d, JPC ¼ 9.9 Hz), 120.91, 119.48, 119.10
(d, JPC ¼ 2.3 Hz), 119.06, 68.91, 63.29 (d, JPC ¼ 9.1 Hz), 45.60 (d,
JPC ¼ 4.6 Hz), 26.34, 22.59, 19.28 ppm. 31P{1H} NMR (C6D6):
(see SI), of which removal was unsuccessful. 1H NMR (C6D6):
d 7.32
(t, 2H), 7.25 (ddd, J ¼ 12, 8.0,1.6 Hz, 2H), 6.92e6.85 (m, 5H), 6.68 (dt,
J ¼ 7.4, 1.2 Hz, 2H), 5.61e5.41 (m, 2H, 2-quinaldine), 2.65e2.50 (m,
2H, 4-quinaldine), 2.30e2.20 (m, 2H, 4-quinaldine), 2.02e1.91 (m,
2H, 3-quinaldine), 1.59e1.50 (m, 2H, 3-quinaldine), 1.35e1.25 (d,
J ¼ 6.8, 6H, CH3) ppm.
d
ꢁ0.133 ppm. Anal. Calcd (C40H41N2PZr): C, 71.50; H, 6.15; N, 4.17.
Found: C, 71.42; H, 5.97; N, 4.46%.