Living Polymerization of Propylene with ansa-Dimethylsilylene(fluorenyl)(cumylamido) Titanium Complexes
Abstract
:1. Introduction
2. Experimental Section
2.1. Materials
2.2. Synthesis of Complexes
2.2.1. Synthesis of (2,7-di-tBu)fluorenyl-cumylamido Titanium Complex (1b)
2.2.2. Synthesis of (3,6-di-tBu)fluorenyl-cumylamido Titanium Complex (1c)
2.2.3. Synthesis of Fluorenyl-(1-methyl-(1-naphthyl)ethyl)amido Titanium Complex (2a)
2.2.4. Synthesis of (2,7-di-tBu)fluorenyl-(1-methyl-(1-naphthyl)ethyl)amido Titanium Complex (2b)
2.3. Polymerization Procedure
2.4. Analytical Procedure
3. Results and Discussion
3.1. Molecular Structure of Complexes
3.2. Propylene Polymerization
4. Conclusions
Supplementary Materials
Acknowledgments
Author Contributions
Conflicts of Interest
References
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Complex | 1a | 1b | 2a | 2b |
---|---|---|---|---|
deposition numbers | CCDC 1539490 | CCDC 1539499 | CCDC 1540563 | CCDC 1539502 |
formula | C26H31NSiTi | C34H47NSiTi | C30H33NSiTi | C38H49NSiTi |
formula weight | 433.51 | 545.71 | 483.56 | 595.77 |
crystal system | Monoclinic | Triclinic | Monoclinic | Triclinic |
space group | P1 21/c1 | P | P1 21/c1 | P |
a (Å) | 8.8160(15) | 10.0609(13) | 12.742(3) | 10.3445(13) |
b (Å) | 27.430(5) | 11.5953(15) | 17.562(4) | 11.8424(16) |
c (Å) | 9.9361(18) | 15.4910(3) | 11.404(2) | 15.4920(3) |
β(deg) | 108.372(4) | 100.124(3) | 95.269(4) | 99.822(4) |
V(Å3) | 2280.3(7) | 1561.1(4) | 2541.1(9) | 1636.8(4) |
Z | 4 | 2 | 4 | 2 |
F(000) | 920 | 588 | 1024 | 640 |
Dcalcd. (g·cm−3) | 1263 | 1161 | 1264 | 1209 |
μ (mm−1) | 0.440 | 0.334 | 0.402 | 0.325 |
theta range for data collection | 2.284° to 30.611° | 2.002° to 30.542° | 1.980° to 30.772° | 1.965° to 25.499° |
reflections collected | 23,087 | 15,856 | 25,451 | 11,599 |
independent reflections | 7002 | 9413 | 7920 | 6105 |
final R indices [I > 2δ(I)] | [R(int) = 0.1147] | [R(int) = 0.0235] | [R(int) = 0.0610] | [R(int) = 0.0569] |
R1 = 0.0512, wR2 = 0.0963 | R1 = 0.0398, wR2 = 0.0940 | R1 = 0.0455, wR2 = 0.1040 | R1 = 0.0508, wR2 = 0.1051 |
Parameter | 1a | 1b | 2a | 2b |
---|---|---|---|---|
Ti(1)–C(1) | 2.241(2) | 2.250(14) | 2.260(19) | 2.267(3) |
Ti(1)–C(2) | 2.409(3) | 2.384(14) | 2.414(19) | 2.413(3) |
Ti(1)–C(3) | 2.586(3) | 2.599(14) | 2.556 | 2.576(3) |
Ti(1)–C(4) | 2.594(3) | 2.615(15) | 2.538 | 2.569(3) |
Ti(1)–C(5) | 2.398(2) | 2.430(15) | 2.396(19) | 2.394(3) |
Ti(1)–N(1) | 1.919(2) | 1.922(12) | 1.922(17) | 1.920(2) |
Ti(1)–Si(1) | 2.836(9) | 2.828(6) | 2.850 | 2.848(11) |
N(1)–Ti(1)–C(1) | 78.35(9) | 78.56(5) | 78.01(7) | 77.74(11) |
Ti(1)–N(1)–Si(1) | 100.88(10) | 100.40(6) | 101.30(8) | 101.76(12) |
N(1)–Si(1)–C(1) | 93.66(10) | 94.20(6) | 93.75(8) | 93.88(13) |
Entry | Cat. | Temp. (°C) | Time (min) | Yield (g) | Activity b | Mn c (×104) | Mw/Mn c | N d (μmol) |
---|---|---|---|---|---|---|---|---|
1 | 1a | 0 | 5 | 3.21 | 1930 | 25.2 | 1.49 | 13 |
2 | 1b | 0 | 5 | 3.46 | 2080 | 23.9 | 1.37 | 14 |
3 | 1c | 0 | 5 | 3.59 | 2150 | 26.1 | 1.58 | 14 |
4 | 1a | 25 | 5 | 4.05 | 2430 | 16.8 | 2.05 | 24 |
5 | 1b | 25 | 5 | 4.06 | 2430 | 19.4 | 1.70 | 21 |
6 | 1c | 25 | 5 | 4.21 | 2530 | 16.6 | 1.93 | 25 |
7 | 2a | 0 | 12 | 0.271 | 69 | 5.18 | 1.18 | 5.2 |
8 | 2b | 0 | 12 | 0.084 | 21 | 1.73 | 1.16 | 4.9 |
9 | 2a | 25 | 12 | 0.474 | 119 | 4.81 | 1.43 | 9.9 |
10 | 2b | 25 | 12 | 0.362 | 91 | 4.38 | 1.27 | 8.3 |
Catalyst | Fluorenyl | N-alkyl | θ (°) |
---|---|---|---|
1a | Flu | Ph | 86 |
1b | 2,7-di-tBu-Flu | Ph | 90 |
2a | Flu | Naphthyl | 103 |
2b | 2,7-di-tBu-Flu | Naphthyl | 102 |
Entry | Stereosequence distribution a | ||||||||
---|---|---|---|---|---|---|---|---|---|
mmmm | mmmr | rmmr | mmrr | mmrm + rmrr | rmrm | rrrr | mrrr | mrrm | |
4 | 0.04 | 0.05 | 0.06 | 0.22 | 0.22 | 0.13 | 0.09 | 0.14 | 0.05 |
5 | 0.02 | 0.03 | 0.04 | 0.18 | 0.22 | 0.11 | 0.15 | 0.19 | 0.06 |
6 | 0.03 | 0.05 | 0.03 | 0.13 | 0.20 | 0.14 | 0.16 | 0.21 | 0.05 |
10 | 0.12 | 0.10 | 0.08 | 0.29 | 0.16 | 0.05 | 0.03 | 0.08 | 0.09 |
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Wang, H.; Wang, X.; Sun, Y.; Cheng, H.; Shiono, T.; Cai, Z. Living Polymerization of Propylene with ansa-Dimethylsilylene(fluorenyl)(cumylamido) Titanium Complexes. Polymers 2017, 9, 131. https://doi.org/10.3390/polym9040131
Wang H, Wang X, Sun Y, Cheng H, Shiono T, Cai Z. Living Polymerization of Propylene with ansa-Dimethylsilylene(fluorenyl)(cumylamido) Titanium Complexes. Polymers. 2017; 9(4):131. https://doi.org/10.3390/polym9040131
Chicago/Turabian StyleWang, Huajin, Xinwei Wang, Yanjie Sun, Hailong Cheng, Takeshi Shiono, and Zhengguo Cai. 2017. "Living Polymerization of Propylene with ansa-Dimethylsilylene(fluorenyl)(cumylamido) Titanium Complexes" Polymers 9, no. 4: 131. https://doi.org/10.3390/polym9040131