Citation: Anqiu LIU, Long LIN, Dezhi ZHANG, Junyu LEI, Kefeng WANG, Wei ZHANG, Junpeng ZHUANG, Haijun HAO. Synthesis, structures, and catalytic activity of aluminum and zinc complexes chelated by 2-((2,6-dimethylphenyl)amino)ethanolate[J]. Chinese Journal of Inorganic Chemistry, ;2024, 40(4): 791-798. doi: 10.11862/CJIC.20230424 shu

Synthesis, structures, and catalytic activity of aluminum and zinc complexes chelated by 2-((2,6-dimethylphenyl)amino)ethanolate

Anqiu LIU ¹ ,
Long LIN ² ,
Dezhi ZHANG ³ ,
Junyu LEI ² ,
Kefeng WANG ² ,
Wei ZHANG ^2,, ,
Junpeng ZHUANG ¹ ,
Haijun HAO ^1,,

1.
Department of Organic Chemistry, College of Chemistry, Beijing University of Chemical Technology, Beijing 100029, China
2.
Petrochemical Research Institute, PetroChina Company Limited, Beijing 100195, China
3.
PetroChina Harbin Petrochemical Company, Harbin 150056, China

Corresponding author: Wei ZHANG, zhangwei020@pectrochina.com.cn Haijun HAO, hjhao@mail.buct.edu.cn
Received Date: 8 November 2023
Revised Date: 18 December 2023

Figures(4)

Treatment of ArNHCH₂CH₂OH (HL, Ar＝2,6-Me₂C₆H₃) with AlMe₃ and ZnEt₂ resulted in the formation of a bi-aluminum complex, [(Me₂Al)(L)]₂ (1), and a tetra-zinc complex, [EtZn₂(L)₃]₂ (2), respectively. They were characterized by elemental analysis, NMR, and single-crystal X-ray diffraction analysis. Complex 1 is a crystallographically centrosymmetric dimer with an Al₂O₂ core in the solid state, while a Zn₄O₆ core is observed in 2, which can be viewed as two side-by-side cubes missing a pair of opposite vertices. Preliminary catalytic activity tests indicated that the aluminum complex 1 was inactive for the ring-opening polymerization (ROP) of ε-caprolactone, while the zinc complex 2 was a highly active initiator for the ROP of ε-caprolactone and could control the molecular weight distribution of the resulted polymers in narrow ranges.
- ring-opening polymerization,
- aluminum,
- zinc,
- aminoethanol,
- ε-caprolactone
1. [1]
  Chen Y, Hung S T, Chou E, Wu H S. Review of polyhydroxyalkanoates materials and other biopolymers for medical applications[J]. Mini Rev. Org. Chem., 2018,15:105-121. doi: 10.2174/1570193X14666170721153036
2. [2]
  Wei Y, Wang S, Zhou S. Aluminum alkyl complexes: Synthesis, structure, and application in ROP of cyclic esters[J]. Dalton Trans., 2016,45:4471-4485. doi: 10.1039/C5DT04240B
3. [3]
  Gao J, Zhu D, Zhang W, Solan G A, Ma Y, Sun W H. Recent progress in the application of group 1, 2 & 13 metal complexes as catalysts for the ring opening polymerization of cyclic esters[J]. Inorg. Chem. Front., 2019,6:2619-2652.
4. [4]
  Théron B, Vaillant-Coindard V, Balan C, Rousselin Y, Bayardon J, Malacea-Kabbara R, Gendre P L. Al and Zn phenoxy-amidine complexes for lactide ROP catalysis[J]. Dalton Trans., 2023,52:7854-7868. doi: 10.1039/D3DT01216F
5. [5]
  LI W L, YAN B, SUN C G, SHEN Q M, LIU W Q, MA X L, YANG Z. Aluminum amine compound protected by β-diketiminate ligand: Preparation and enhanced performance as catalyst for ring-opening polymerization of ε-caprolactone[J]. Chinese J. Inorg. Chem., 2021,37:151-156. doi: 10.11862/CJIC.2021.007
6. [6]
  Glöckler E, Kapp L, Wölper C, Schumacher M, Gröschel A H, Schulz S. Homoleptic and heteroleptic ketodiiminate zinc complexes for the ROP of cyclic L-lactide[J]. RSC Adv., 2023,13:29879-29885. doi: 10.1039/D3RA06529D
7. [7]
  Chen M T, Chen C T. An unprecedented Zn₁₀O₄ heteroadamantane cage containing anilido-pyridinate ligand and its activity for ring opening polymerization of L-lactide and ε-caprolactone[J]. Dalton Trans., 2017,46:10181-10184. doi: 10.1039/C7DT01925D
8. [8]
  Bouyahyi M, Duchateau R. Metal-based catalysts for controlled ring-opening polymerization of macrolactones: High molecular weight and well-defined copolymer architectures[J]. Macromolecules, 2014,47:517-524. doi: 10.1021/ma402072t
9. [9]
  Albertsson A C, Varma I K. Recent developments in ring opening polymerization of lactones for biomedical applications[J]. Biomacromolecules, 2003,4:1466-1486. doi: 10.1021/bm034247a
10. [10]
  Dechy-Cabaret O, Martin-Vaca B, Bourissou D. Controlled ring-opening polymerization of lactide and glycolide[J]. Chem. Rev., 2004,104:6147-6176. doi: 10.1021/cr040002s
11. [11]
  Darensbourg D J, Karroonnirun O. Stereoselective ring-opening polymerization of rac-lactides catalyzed by chiral and achiral aluminum half-salen complexes[J]. Organometallics, 2010,29:5627-5634. doi: 10.1021/om100518e
12. [12]
  Zhang C, Wang Z X. Aluminum and zinc complexes supported by functionalized phenolate ligands: Synthesis, characterization and catalysis in the ring-opening polymerization of ε-caprolactone and rac-lactide[J]. J. Organomet. Chem., 2008,693:3151-3158. doi: 10.1016/j.jorganchem.2008.07.002
13. [13]
  Press K, Goldberg I, Kol M. Mechanistic insight into the stereochemical control of lactide polymerization by salan-aluminum catalysts[J]. Angew. Chem. Int. Ed., 2015,54:14858-1486. doi: 10.1002/anie.201503111
14. [14]
  Cross E D, Allan L E N, Decken A, Shaver M P. Aluminum salen and salan complexes in the ring-opening polymerization of cyclic esters: Controlled immortal and copolymerization of rac-β-butyrolactone and rac-lactide[J]. J. Polym. Sci. Part A: Polym. Chem., 2013,51:1137-1146. doi: 10.1002/pola.26476
15. [15]
  Pepels M P F, Bouyahyi M, Heise A, Duchateau R. Kinetic investigation on the catalytic ring-opening (co)polymerization of (macro)lactones using aluminum salen catalysts[J]. Macromolecules, 2013,46:4324-4334. doi: 10.1021/ma400731c
16. [16]
  Yang X Z, Wang L, Yao L H, Zhang J F, Tang N, Wang C, Wu J C. Synthesis, characterization of bulky aluminium alkoxide and application in the ring-opening polymerization of ε-caprolactone[J]. Inorg. Chem. Commun., 2011,14:1711-1714. doi: 10.1016/j.inoche.2011.07.012
17. [17]
  Liao T C, Huang Y L, Huang B H, Lin C C. Alcoholysis of methyl aluminium biphenoxides: Excellent initiators for the ring opening polymerisation of ε-caprolactone[J]. Macromol. Chem. Phys., 2003,204:885-892. doi: 10.1002/macp.200390054
18. [18]
  Qiao S, Ma W A, Wang Z X. Synthesis and characterization of aluminum and zinc complexes supported by pyrrole-based ligands and catalysis of the aluminum complexes toward the ring-opening polymerization of ε-caprolactone[J]. J. Organomet. Chem., 2011,696:2746-2753. doi: 10.1016/j.jorganchem.2011.04.028
19. [19]
  Liu Y, Dong W S, Liu J Y, Li Y S. Living ring-opening homo- and copolymerisation of ε-caprolactone and L-lactide by cyclic β-ketiminato aluminium complexes[J]. Dalton Trans., 2014,43:2244-2251. doi: 10.1039/C3DT52712C
20. [20]
  Xiao L, Zhao Y, Qiao S, Sun Z, Santoro O, Redshaw C. Synthesis and structures of mono- and dinuclear aluminium and zinc complexes bearing α-diimine and related ligands, and their use in the ring opening polymerization of cyclic esters[J]. Dalton Trans., 2020,49:1456-1472. doi: 10.1039/C9DT04332B
21. [21]
  Chuang H J, Chen H L, Huang B H, Tsai T E, Huang P L, Liao T T, Lin C C. Efficient zinc initiators supported by NNO-tridentate ketiminate ligands for cyclic esters polymerization[J]. J. Polym. Sci. Part A: Polym. Chem., 2013,51:1185-1196. doi: 10.1002/pola.26486
22. [22]
  Huang T L, Chen C T. Aluminium complexes containing pyrazolyl-phenolate ligands as catalysts for ring opening polymerization of ε-caprolactone[J]. J. Organomet. Chem., 2013,725:15-21. doi: 10.1016/j.jorganchem.2012.12.003
23. [23]
  Sun W H, Shen M, Zhang W, Huang W, Liu S, Redshaw C. Methylaluminium 8-quinolinolates: synthesis, characterization and use in ring-opening polymerization (ROP) of ε-caprolactone[J]. Dalton Trans., 2011,40:2645-2653. doi: 10.1039/c0dt01207f
24. [24]
  Chen C T, Liao C H, Peng K F, Chen M T, Huang T L. Synthesis, characterization and catalytic studies of aluminium complexes containing sulfonamido-oxazolinate or - pyrazolinate ligands[J]. J. Organomet. Chem., 2014,753:9-19. doi: 10.1016/j.jorganchem.2013.12.022
25. [25]
  Ma W A, Wang Z X. Zinc and aluminum complexes supported by quinoline-based N, N, N-chelate ligands: Synthesis, characterization, and catalysis in the ring-opening polymerization of ε-caprolactone and rac-lactide[J]. Organometallics, 2011,30:4364-4373. doi: 10.1021/om200423g
26. [26]
  Yu X F, Wang Z X, Han Z Y. Synthesis and structural characterisation of dinuclear aluminium complexes supported by NNO-tridentate Schiff-base ligands and their catalysis in the ring-opening polymerisation of ε-caprolactone[J]. ChemistrySelect, 2021,6:3403-3408. doi: 10.1002/slct.202100635
27. [27]
  Gao B, Duan R L, Pang X, Li X, Qu Z, Shao H L, Wang X H, Chen X S. Zinc complexes containing asymmetrical N, N, O-tridentate ligands and their application in lactide polymerization[J]. Dalton Trans., 2013,42:16334-16342. doi: 10.1039/c3dt52016a
28. [28]
  Chen C T, Chan C Y, Huang C A, Chen M T, Peng K F. Zinc anilido-oxazolinate complexes as initiators for ring opening polymerization[J]. Dalton Trans., 2007:4073-4078.
29. [29]
  Montag M, Milstein D. Catalytic main-group metal complexes of phosphine-based pincer ligands[J]. Isr. J. Chem., 2023,63e202300082. doi: 10.1002/ijch.202300082
30. [30]
  HUANG Q D, LI C L, ZHANG Y, CUI L S, ZHU B C, YI J J, LIU L, HAO H J. Synthesis and catalytic activity of aluminum complexes supported by bis(β-ketimine) and bis(β-diketimine) ligands[J]. Chem. J. Chinese Universities, 2014,35:524-530. doi: 10.7503/cjcu20130664
31. [31]
  Zelga K, Pietrzak T, Han T, Justyniak I, Chwojnowska E, Sobota P, Lewiński J. Effectiveness of the oxygenation over classical protonolysis reactions: A case of alkylzinc complexes incorporating an aminoalcoholate ligand[J]. Chem.-Eur. J., 2021,27:14234-14239. doi: 10.1002/chem.202102172
32. [32]
  Rhodes B, Chien J C W, Wood J S, Chandrasekaran A, Rausch M D. Synthesis of titanium(Ⅳ) complexes containing 2,6-dimethylaniline substituted amino alcohols and their utilization in ethylene polymerizations[J]. J. Organomet. Chem., 2001,625:95-100. doi: 10.1016/S0022-328X(00)00907-4
33. [33]
  Nakano K, Nozaki K, Hiyama T. Asymmetric alternating copolymerization of cyclohexene oxide and CO₂ with dimeric zinc complexes[J]. J. Am. Chem. Soc., 2003,125:5501-5510. doi: 10.1021/ja028666b
34. [34]
  Cao F, Wang Y, Wang X, Zhang W J, Solan G A, Wang R, Ma Y P, Hao X, Sun W H. Zinc 8-aminotrihydroquinolines appended with pendant N-diphenylphosphinoethyl arms as exceptionally active catalysts for the ROP of ε-CL[J]. Catal. Sci. Technol., 2022,12:6687-6703. doi: 10.1039/D2CY00979J
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