Citation: WU Cheng, XIAO Chunsheng, CHEN Xuesi. Application of Frustrated Lewis Pairs in Polymerization[J]. Chinese Journal of Applied Chemistry, ;2018, 35(9): 1013-1018. doi: 10.11944/j.issn.1000-0518.2018.09.180178 shu

Application of Frustrated Lewis Pairs in Polymerization

WU Cheng ^a,b ,
XIAO Chunsheng ^a,, ,
CHEN Xuesi ^a,,

a.
Key Laboratory of Polymer Ecomaterials, Changchun Institute of Applied Chemistry, Chinese Academy of Sciences, Changchun 130022, China
b.
University of Chinese Academy of Sciences, Beijing 100049, China

Corresponding author: XIAO Chunsheng, xiaocs@ciac.ac.cn CHEN Xuesi, xschen@ciac.ac.cn
Received Date: 15 May 2018
Revised Date: 28 May 2018
Accepted Date: 4 June 2018

Fund Project: Supported by the National Natural Science Foundation of China(No.51773196, No.51573184, No.51520105004), the Chinese Academy of Sciences Youth Innovation Promotion Project(No.2017266)the National Natural Science Foundation of China 51773196the National Natural Science Foundation of China 51520105004the Chinese Academy of Sciences Youth Innovation Promotion Project 2017266the National Natural Science Foundation of China 51573184

Figures(8)

Frustrated Lewis pairs (FLPs) are combinations of bulky Lewis acids and bulky Lewis bases in solution that are deterred to from dative bonds by steric factors. In this particular combination, Lewis acids and Lewis bases failed to be neutralized and quenched, and remained reactive. When small molecules such as H₂ are close to them, FLPs can split the chemical bonds of H₂ to obtain a cation and an anion. This particular reaction activity shows promising applications of FLPs in catalytic hydrogenation, activation of small molecules, olefin polymerization, ring-opening polymerization and so on. Especially, in olefin polymerization and ring-opening polymerization, FLPs have a strong catalytic activity. In this article, we briefly introduce the development history of FLPs and the application of FLPs in activation of small molecules. In addition, the applications of FLPs in polymer fields are emphatically described.
- frustrated Lewis pairs,
- catalyst,
- polymerization,
- activation of small molecules
1. [1]
  Stephan D W, Erker G. Frustrated Lewis Pairs:Metal-Free Hydrogen Activation and More[J]. Angew Chem Int Ed, 2010,49(1):46-76. doi: 10.1002/anie.200903708
2. [2]
  Stephan D W, Erker G. Frustrated Lewis Pair Chemistry:Development and Perspectives[J]. Angew Chem Int Ed, 2015,54(22):6400-6441. doi: 10.1002/anie.201409800
3. [3]
  Spies P, Erker G, Kehr G. Rapid Intramolecular Heterolytic Dihydrogen Activation by a Four-Membered Heterocyclic Phosphane-Borane Adduct[J]. Chem Commun, 2007,47(47):5072-5074.
4. [4]
  Stephan D W, Erker G. Frustrated Lewis Pairs:Metal-Free Hydrogen Activation and More[J]. Angew Chem Int Ed, 2010,49(1):46-76. doi: 10.1002/anie.200903708
5. [5]
  Stephan D W, Erker G. Frustrated Lewis Pair Chemistry:Development and Perspectives[J]. Angew Chem Int Ed, 2015,54(22):6400-6441. doi: 10.1002/anie.201409800
6. [6]
  Liu L, Cao L L, Shao Y. A Radical Mechanism for Frustrated Lewis Pair Reactivity[J]. Chemistry, 2017,3(2):259-267. doi: 10.1016/j.chempr.2017.05.022
7. [7]
  XU Tieqi, LI Changhong. Application of Lewis Pairs in the Polymerization[J]. Chinese Prog Chem, 2015,27(8):1087-1092.
8. [8]
  XU Yingying, LI Zhao, Maxim Borzov. Application of Frustrated Lewis Pairs in the Activation of Small Molecules[J]. Chinese Prog Chem, 2012,24(8):1526-1532.
9. [9]
  YANG Hanyu, YANG Zhongtian, YU Zhidi. Research Progress on Frustrated Lewis Pairs Chemistry[J]. Chinese Univ Chem, 2016,31(4):1-11.
10. [10]
  Mccahill J S J, Welch G C, Stephan D W. Reactivity of "Frustrated Lewis Pairs":Three-Component Reactions of Phosphines, a Borane, and Olefins[J]. Angew Chem Int Ed, 2007,46(26):4968-4971. doi: 10.1002/(ISSN)1521-3773
11. [11]
  PENG Bin, NIE Yong. Chinese Translation of "Frustratede Lewis Pair"[J]. China Terminol,, 2010,12(6):44-49. doi: 10.3969/j.issn.1673-8578.2010.06.015
12. [12]
  Greb L, Ona-Burgos P, Schirmer B. Metal-Free Catalytic Olefin Hydrogenation:Low-Temperature H₂ Activation by Frustrated Lewis Pairs[J]. Angew Chem Int Ed, 2012,51(40):10164-10168. doi: 10.1002/anie.201204007
13. [13]
  LIU Yongbing, DU Haifeng. Frustrated Lewis Pair Catalyzed Asymmetric Hydrogenation[J]. Chinese Acta Chim Sin, 2014,72(7):771-777.
14. [14]
  Chernichenko K, Madarasz A, Papai I. A Frustrated-Lewis-Pair Approach to Catalytic Reduction of Alkynes to Cis-Alkenes[J]. Nat Chem, 2013,5(8):718-723. doi: 10.1038/nchem.1693
15. [15]
  Momming C M, Otten E, Kehr G. Reversible Metal-Free Carbon Dioxide Binding by Frustrated Lewis Pairs[J]. Angew Chem Int Ed, 2009,48(36):6643-6646. doi: 10.1002/anie.v48:36
16. [16]
  Otten E, Neu R C, Stephan D W. Complexation of Nitrous Oxide by Frustrated Lewis Pairs[J]. J Am Chem Soc, 2009,131(29):9918-9919. doi: 10.1021/ja904377v
17. [17]
  Sajid M, Klose A, Birkmann B. Reactions of Phosphorus/Boron Frustrated Lewis Pairs with SO₂[J]. Chem Sci, 2013,4(1):213-219. doi: 10.1039/C2SC21161K
18. [18]
  Sajid M, Stute A, Cardenas A J P. N, N-Addition of Frustrated Lewis Pairs to Nitric Oxide:An Easy Entry to a Unique Family of Aminoxyl Radicals[J]. J Am Chem Soc, 2012,134(24):10156-10168. doi: 10.1021/ja302652a
19. [19]
  Kreitner C, Geier S J, Stanlake L J E. Ring Openings of Lactone and Ring Contractions of Lactide by Frustrated Lewis Pairs[J]. Dalton Trans, 2011,40(25):6771-6777. doi: 10.1039/c1dt10449g
20. [20]
  Birkmann B, Voss T, Geier S J. Frustrated Lewis Pairs and Ring-Opening of THF, Dioxane, and Thioxane[J]. Organometallics, 2010,29(21):5310-5319. doi: 10.1021/om1003896
21. [21]
  Zhang Y, Miyake G M, Chen E Y. Alane-Based Classical and Frustrated Lewis Pairs in Polymer Synthesis:Rapid Polymerization of MMA and Naturally Renewable Methylene Butyrolactones into High-Molecular-Weight Polymers[J]. Angew Chem Int Ed, 2010,49(52):10158-10162. doi: 10.1002/anie.201005534
22. [22]
  Chen E, He J, Zhang Y. Synthesis of Pyridine-and 2-Oxazoline-Functionalized Vinyl Polymers by Alane-Based Frustrated Lewis Pairs[J]. Synlett, 2014,25(11):1534-1538. doi: 10.1055/s-00000083
23. [23]
  Xu T, Chen E Y X. Probing Site Cooperativity of Frustrated Phosphine/Borane Lewis Pairs by a Polymerization Study[J]. J Am Chem Soc, 2014,136(5):1774-1777. doi: 10.1021/ja412445n
24. [24]
  Chen J, Chen E Y X. Lewis Pair Polymerization of Acrylic Monomers by N-Heterocyclic Carbenes and B(C₆F₅)₃[J]. Isr J Chem, 2015,55(2):216-225. doi: 10.1002/ijch.v55.2
25. [25]
  Holtrichter-Roessmann T, Isermann J, Roesener C. An Aluminum-Nitrogen Based Lewis Pair as an Effective Catalyst for the Oligomerization of Cyanamides:Formation of Acyclic C-N Oligomers Instead of Thermodynamically Favored Cyclic Aromatic Trimers[J]. Angew Chem Int Ed, 2013,52(28):7135-7138. doi: 10.1002/anie.201301970
26. [26]
  Wang M, Nudelman F, Matthes R. Frustrated Lewis Pair Polymers as Responsive Self-Healing Gels[J]. J Am Chem Soc, 2017,139(40):14232-14236. doi: 10.1021/jacs.7b07725
27. [27]
  Pang X, Duan R, Li X. Bimetallic Salen-Aluminum Complexes:Synthesis, Characterization and Their Reactivity with Rac-Lactide and ε-Caprolactone[J]. Polym Chem, 2014,5(12):3894-3900. doi: 10.1039/c3py01774e
28. [28]
  Duan R, Gao B, Li X. Zinc Complexes Bearing Tridentate O, N, O-Type Half-Salen Ligands for Ring-Opening Polymerization of Lactide[J]. Polymer, 2015,71(5):1-7.
29. [29]
  Duan R, Hu C, Li X. Air-Stable Salen-Iron Complexes:Stereoselective Catalysts for Lactide and ε-Caprolactone Polymerization Through in Situ Initiation[J]. Macromolecules, 2017,50(23):9188-9195. doi: 10.1021/acs.macromol.7b01766
30. [30]
  Piedra-Arroni E, Ladaviere C, Amgoune A. Ring-Opening Polymerization with Zn(C₆F₅)₂-Based Lewis Pairs:Original and Efficient Approach to Cyclic Polyesters[J]. J Am Chem Soc, 2013,135(36):13306-13309. doi: 10.1021/ja4069968
31. [31]
  Nakayama Y, Kosaka S, Yamaguchi K. Controlled Ring-Opening Polymerization of L-Lactide and Epsilon-Caprolactone Catalyzed by Aluminum-Based Lewis Pairs or Lewis Acid Alone[J]. J Polym Sci, Part A:Polym Chem, 2017,55(2):297-303. doi: 10.1002/pola.v55.2
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