Cited by 49biodegradable polymer synthesis and propertiesOrganometallic Complex Synthesis and CatalysisCarbon dioxide utilization in catalysis

Reverse orders of reactivities in the polymerization of cyclic esters using N 2 O 2 aluminium alkoxide complexes

Phomphrai, Khamphee, Chumsaeng, Phongnarin, Sangtrirutnugul, Preeyanuch, Kongsaeree, Palangpon, Pohmakotr, Manat·2010·Dalton Trans.

Abstract

Three aluminium alkoxide complexes containing N(2)O(2) bis(phenoxy)-amine ligands were synthesized from reactions of the corresponding N(2)O(2) ligands with Al(O(i)Pr)(3) in toluene. Different amine side chains of the ligands included pyridine (1), CH(2)NMe(2) (2), and CH(2)NEt(2) (3). The related chloro aluminium analog (4) was prepared from a reaction between AlCl(3) and the potassium salt of the N(2)O(2) ligand having CH(2)NMe(2) side chain. X-Ray crystallography reveals that complexes 3 and 4 have a monomeric five-coordinate aluminium center. Complexes 1-3 catalyzed the polymerization of epsilon-caprolactone (epsilon-CL) at 70 degrees C in toluene with the relative reactivities of 1<2< 3. In contrary, only complex 1 was active for the polymerization of lactide under the same polymerization conditions. (1)H NMR spectroscopy shows that treatment of 2 with 1 equivalent of lactide afforded the ring-opened product L(2)Al-OCH(Me)C(O)OCH(Me)C(O)O(i)Pr. Electronic effects are believed to be responsible for the observed trend in the epsilon-CL polymerization rates. On the other hand, steric hindrance at the amine side chain is the main contributor to the observed rates of lactide polymerization.

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Crossref · 10.1039/b919340e

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Authors
Phomphrai, K., Chumsaeng, P., Sangtrirutnugul, P., Kongsaeree, P., & Pohmakotr, M.
Affiliations
Mahidol University (TH)
Corresponding author
Phomphrai, Khamphee
Venue
Dalton Trans.
Published
2010
Volume
39
Issue
7
Pages
1865-1871
ISSN
  • 1477-9226 (ISSN-L)
  • 1477-9234
OpenAlex
W2004710638
Cited by
49
References
22
Citations by year
2025: 1 · 2024: 2 · 2023: 3 · 2022: 4 · 2021: 1 · 2020: 1 · 2019: 4 · 2018: 5 · 2017: 5 · 2016: 1 · 2015: 4 · 2014: 5 · 2013: 5 · 2012: 4
FWCI
1.17
Type
journal article
Language
en
Open access
closed
Locations
  • Dalton Transactions (publishedVersion)
  • PubMed (publishedVersion)
Funders
  • Thailand Research Fund
  • Commission on Higher Education
  • Center of Excellence for Innovation in Chemistry
Topics
  • Physical Sciences › Materials Science › Biomaterials › biodegradable polymer synthesis and properties
  • Physical Sciences › Chemistry › Organic Chemistry › Organometallic Complex Synthesis and Catalysis
  • Physical Sciences › Chemical Engineering › Process Chemistry and Technology › Carbon dioxide utilization in catalysis
Keywords
cyclic ester polymerization, ε-caprolactone, lactide, ring-opening polymerization, catalytic activity, steric hindrance, electronic effects, pyridine ligands
MeSH terms
Aluminum, Cyclization, Esters, Models, Molecular, Nitrogen Oxides, Organometallic Compounds, Stereoisomerism, Molecular Structure, Crystallography, X-Ray

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