Kinetics, Mechanism and Theoretical Studies of Norbornene-Ethylene Alternating Copolymerization Catalyzed by Organopalladium(II) Complexes Bearing Hemilabile α-Amino–pyridine
Abstract
:1. Introduction
2. Results and Discussion
2.1. Synthesis and Characterization of Norbornyl Palladium Complexes
2.2. Geometrical Isomerisation of Norbornylpalladium Complex
2.3. Kinetics of Norbornene Insertion Reactions in Organopalladium(II) Complexes
2.4. Kinetics of Ethylene Insertion Reactions in Organopalladium(II) Complexes
2.5. DFT Approach for E–N Copolymerization
2.5.1. C–T Isomerization
2.5.2. Ethylene Insertion into (C2H4)Pd-Me
2.5.3. Norbornene Insertion into (C2H4)Pd-Me.
2.5.4. Ethylene and Norbornene Insertion into (C2H4)Pd-C7H10Me
2.5.5. Mechanism of Alternating E–N Copolymerization
3. Materials and Methods
3.1. Materials
3.2. Measurements
4. Conclusions
Supplementary Materials
Acknowledgments
Author Contributions
Conflicts of Interest
References
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RHNCH2(o-C6H4N) | Me-Pd [8] | MeC7H10-Pd | ||||
---|---|---|---|---|---|---|
R | T (%) | C (%) | T (%) (anti/syn) | C (%) | ||
iPr | 1a | 82 | 18 | 2a | 100 (30/70) | 0 |
tBu | 1b | 100 | 0 | 2b | 100 (27/73) | 0 |
Ph | 1c | 93 | 7 | 2c | 96 (41/55) | 4 |
2,6-Me2C6H3 | 1d | 60 | 40 | 2d | 87 (47/40) | 13 |
2,6-iPr2C6H3 | 1e | 62 | 38 | 2e | 94 (44/50) | 6 |
Entry | Cat | Temp. (K) | [Cat] (×10−3 M) | [N] a/[Cat] | kobs (10−4 s−1) | |
---|---|---|---|---|---|---|
C | T | |||||
1 | 1a | 263 | 5.3 | 28.7 | - b | 8.69 |
2 | 1b | 263 | 24.9 | 82.2 | - c | 2.40 |
3 | 1c | 263 | 2.0 | 23.2 | - b | 51.60 |
4 | 1d | 263 | 1.1 | 16.7 | 134.00 | 21.80 |
5 | 1e | 263 | 3.4 | 10.8 | - b | 5.47 |
6 | 1e | 263 | 3.4 | 24.2 | - b | 6.19 |
7 | 1e | 263 | 3.4 | 62.6 | - b | 10.10 |
8 | 1e | 263 | 3.4 | 134.5 | - b | 12.90 |
9 | 1e | 263 | 3.4 | 260.9 | - b | 23.80 |
10 | 1e | 263 | 1.7 | 21.0 | 110.00 | - |
11 | 1e | 258 | 3.3 | 31.1 | 109.00 | 2.35 |
12 | 1e | 253 | 3.4 | 26.3 | 41.30 | 1.29 |
13 | 1e | 243 | 3.3 | 28.0 | 16.80 | - |
14 | 1e | 238 | 3.4 | 27.2 | 9.68 | - |
15 | 1e | 233 | 3.3 | 20.1 | 7.11 | - |
16 | 1e | 233 | 3.3 | 33.7 | 10.80 | - |
17 | 1e | 233 | 3.3 | 40.5 | 12.90 | - |
18 | 1e | 228 | 3.4 | 31.3 | 2.50 | - |
RHNCH2(o-C6H4N) | E-Coord. Complexes | |||||
---|---|---|---|---|---|---|
R | T (%) | C (%) | T (%) | C (%) | ||
iPr | 1a’ | 58 | 42 | 5a’ | 59 | 41 |
tBu | 1b’ | 63 | 37 | 5b’ | 58 | 42 |
Ph | 1c’ | 100 | 0 | 5c’ | 100 | 0 |
2,6-Me2C6H3 | 1d’ | 59 | 41 | 5d’ | 64 | 36 |
2,6-iPr2C6H3 | 1e’ | 38 | 62 | 5e’ | 67 | 33 |
Entry | Temp. (K) | Cat | [Cat] (10−3 M) | [E] a/[Cat] | kE (10−4 s−1) | ||
---|---|---|---|---|---|---|---|
C | T | Total b | |||||
1 | 263 | 1a | 5.3 | 18.3 | c | c | 6.44 |
2 | 263 | 1b | 3.6 | 21.3 | d | 8.05 | - |
3 | 263 | 1c | 4.4 | 25.9 | e | 1.93 | - |
4 | 263 | 1d | 3.2 | 17.7 | 4.74 | 4.72 | 4.28 |
5 | 268 | 1e | 3.4 | 21.7 | 13.10 | 14.30 | 13.60 |
6 | 263 | 1e | 3.3 | 14.3 | 4.36 | 3.80 | 4.14 |
7 | 263 | 1e | 3.3 | 25.0 | 4.46 | 4.19 | 4.37 |
8 | 263 | 1e | 3.3 | 51.9 | 4.91 | 4.27 | 4.71 |
9 | 258 | 1e | 3.4 | 49.4 | 3.40 | 3.20 | 3.37 |
10 | 253 | 1e | 3.4 | 32.5 | 1.16 | 1.17 | 1.16 |
11 | 243 | 1e | 3.3 | 27.2 | 0.41 | 0.41 | 0.41 |
Cat | Act. b | NBcoc c (mol %) | Single c (mol %) | Diads c (mol %) | Triads c (mol %) | Alter. c (mol %) |
---|---|---|---|---|---|---|
1a | 14 | 44.0 | 33.7 | 6.9 | 3.4 | 76.6 |
1b | 5 | 42.9 | 39.0 | 3.9 | 0 | 81.9 |
1c | 6 | 47.5 | 26.4 | 12.4 | 8.7 | 71.0 |
1d | 27 | 48.1 | 34.8 | 6.9 | 6.4 | 80.8 |
1e | 28 | 49.0 | 38.7 | 6.1 | 4.2 | 86.3 |
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Yu, K.-H.; Huang, S.-L.; Liu, Y.-H.; Wang, Y.; Liu, S.-T.; Cheng, Y.-C.; Lin, Y.-F.; Chen, J.-T. Kinetics, Mechanism and Theoretical Studies of Norbornene-Ethylene Alternating Copolymerization Catalyzed by Organopalladium(II) Complexes Bearing Hemilabile α-Amino–pyridine. Molecules 2017, 22, 1095. https://doi.org/10.3390/molecules22071095
Yu K-H, Huang S-L, Liu Y-H, Wang Y, Liu S-T, Cheng Y-C, Lin Y-F, Chen J-T. Kinetics, Mechanism and Theoretical Studies of Norbornene-Ethylene Alternating Copolymerization Catalyzed by Organopalladium(II) Complexes Bearing Hemilabile α-Amino–pyridine. Molecules. 2017; 22(7):1095. https://doi.org/10.3390/molecules22071095
Chicago/Turabian StyleYu, Kuo-Hsuan, Shou-Ling Huang, Yi-Hung Liu, Yu Wang, Shiuh-Tzung Liu, Yuan-Chung Cheng, Ya-Fan Lin, and Jwu-Ting Chen. 2017. "Kinetics, Mechanism and Theoretical Studies of Norbornene-Ethylene Alternating Copolymerization Catalyzed by Organopalladium(II) Complexes Bearing Hemilabile α-Amino–pyridine" Molecules 22, no. 7: 1095. https://doi.org/10.3390/molecules22071095