Synthesis and Structural Studies of Heterobimetallic Alkoxide Complexes Supported by Bis(phenolate) Ligands: Efficient Catalysts for Ring-Opening Polymerization of l -Lactide
Abstract
A series of heterobimetallic titanium(IV) complexes [LTi(O(i)Pr)(mu-O(i)Pr)(2)Li(THF)(2)], [LTi(O(i)Pr)(mu-O(i)Pr)(2)Na(THF)(2)], [LTi(mu-O(i)Pr)(2)Zn(O(i)Pr)(2)], and [LTi(mu-O(i)Pr)(2)Mg(O(i)Pr)(2)] (where L = bidentate bisphenol ligands) have been synthesized and characterized including a structural determination of [L(1)Ti(mu(2)-O(i)Pr)(2)(O(i)Pr)Li(THF)(2)] (1a). These complexes were investigated for their utility in the ring-opening polymerization (ROP) of l-lactide (LA). Polymerization activities have been shown to correlate with the electronic properties of the substituent within the bisphenol ligand. In contrast to monometallic titanium initiator 1e, all the heterobimetallic titanium initiators (Ti-Li, Ti-Na, Ti-Zn, and Ti-Mg) show enhanced catalytic activity toward ring-opening polymerization (ROP) of l-LA. In addition, the use of electron-donating methoxy or methylphenylsulfonyl functional ligands reveals the highest activity. The bisphenol bimetallic complexes give rise to controlled ring-opening polymerization, as shown by the linear relationship between the percentage conversion and the number-average molecular weight. The polymerization kinetics using 2c as an initiator were also studied, and the experimental results indicate that the reaction rate is first-order with respect to both monomer and catalyst concentration with a polymerization rate constant, k = 81.64 M(-1) min(-1).
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Dinuclear complexes 88 and 89 exhibited higher catalytic activity than did mononuclear complex 90 (7 and 4 times as high for CL polymerization for kobs values) and still maintained the same controllability as mononuclear complex 90.
“Dinuclear complexes 88 and 89 exhibited higher catalytic activity than did mononuclear complex 90 (7 and 4 times as high for CL polymerization for k obs values) and still maintained the same controllability as mononuclear complex 90.”
From Multinuclear metal catalysts in ring-opening polymerization of ε‑caprolactone and lactide: Cooperative and electronic effects between metal centers (2023) · cites this paper as [99]
The dramatic increase of the dinuclear Al complexes can be attributed to the electronic connection between two Al centers.
“The dramatic increase of the dinuclear Al complexes can be attributed to the electronic connection between two Al centers.”
From Multinuclear metal catalysts in ring-opening polymerization of ε‑caprolactone and lactide: Cooperative and electronic effects between metal centers (2023) · cites this paper as [99]
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- Authors
- Chen, H.-Y., Liu, M.-Y., Sutar, A. K., & Lin, C.-C.
- Affiliations
- National Chung Hsing University (TW)
- Department of Chemistry, National Chung Hsing University, Taichung 402, Taiwan, Republic of China
- Corresponding author
- Lin, Chu-Chieh
- Venue
- Inorganic Chemistry
- Publisher
- American Chemical Society (ACS)
- Published
- 2009-12-16
- Volume
- 49
- Issue
- 2
- Pages
- 665-674
- ISSN
- 0020-1669 (ISSN-L)
- 1520-510X
- OpenAlex
- W1967491248
- Cited by
- 95
- References
- 85
- Citations by year
- 2026: 1 · 2024: 4 · 2023: 3 · 2022: 5 · 2021: 3 · 2020: 8 · 2019: 2 · 2018: 6 · 2017: 8 · 2016: 11 · 2015: 7 · 2014: 6 · 2013: 14 · 2012: 8
- FWCI
- 2.49
- Type
- journal article
- Language
- en
- Open access
- closed
- Locations
- Inorganic Chemistry (publishedVersion)
- PubMed (publishedVersion)
- 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
- ring-opening polymerization, L-lactide, poly(L-lactic acid), controlled ring-opening polymerization, polymerization kinetics, polymerization rate constants, ligand electronic effects, polymerization activity
- MeSH terms
- Catalysis, Dioxanes, Models, Molecular, Phenols, Polyesters, Titanium, Molecular Structure
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