Heterometallic cooperativity in divalent metal prophenol catalysts: combining zinc with magnesium or calcium for cyclic ester ring-opening polymerisation
Open accessAbstract
The first heterobimetallic lactide ROP catalysts based on two divalent metals outperform the homobimetallic analogues, attributed to the increased Lewis acidity of Mg or Ca (monomer coordination) and enhanced polarity of Zn–Et/OR (propagation).
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The results revealed the heterometals cooperated, with Lewis acidic Na or K to activate the carbonyl group of LA towards nucleophilic attack from benzyl alkoxide on Mg or Ca.
“The results revealed the heterometals cooperated, with Lewis acidic Na or K to activate the carbonyl group of LA towards nucleophilic attack from benzyl alkoxide on Mg or Ca.”
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 [90]
The Conclusions (page unavailable) propose the opposite assignment: Lewis-acidic Mg or Ca coordinates the monomer, while Zn is the likely source of the nucleophile. The paper discusses Na/Zn and K/Zn catalysts as comparators, not Na or K activating LA for attack by an alkoxide on Mg or Ca. (LLM, conf=0.90)
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Experimental — accuracy not yet measuredAlthough heterometallic complexes 61 and 63 exhibited the poor controllability for producing rac-PLA with broad Ð values (1.83 for complex 61 and 1.51 for complex 63), their controllability was greater than those of homometallic complexes 64 and 65.
“Although heterometallic complexes 61 and 63 exhibited the poor controllability for producing rac-PLA with broad Ð values (1.83 for complex 61 and 1.51 for complex 63), their controllability was greater than those of homometallic complexes 64 and 65.”
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 [90]
In “Reactivity insights: molecular weight control and the effect of HMDSH” (page unavailable), the paper describes its heterobimetallic complexes 1 and 2 as relatively well-controlled, with narrow dispersities—not as poorly controlled. It reports that complex 2 was more controlled than the bis-Ca analogue 7, but complex 1 had dispersities comparable to the bis-Mg analogue 6. The cited text does not support the claimed Ð values of 1.83 and 1.51 for the heterometallic complexes. (LLM, conf=0.88)
Experimental — accuracy not yet measuredThe mixtures created by combining complex 64 with 1 eq. Mg(OBn)2 or complex 65 with Ca(OBn)2 outperformed the homometallic constituents (complex 64 and complex 65) and demonstrated similar catalytic activity to heterometallic complexes 61-63.
“The mixtures created by combining complex 64 with 1 eq.Mg(OBn) 2 or complex 65 with Ca(OBn) 2 outperformed the homometallic constituents (complex 64 and complex 65) and demonstrated similar catalytic activity to heterometallic complexes 61-63.”
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 [90]
The benchmarking discussion (page unavailable) reports that the Ca/Zn complex outperformed its homobimetallic counterparts and that the Mg/Zn complex outperformed the bis-Mg counterpart. It does not establish that mixtures made by adding Mg(OBn)₂ or Ca(OBn)₂ to complexes 64 or 65 outperformed those complexes or had activity similar to heterometallic complexes 61–63. (LLM, conf=0.76)
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- Authors
- Gruszka, W., Sha, H., Buchard, A., & Garden, J. A.
- Affiliations
- University of Edinburgh (GB)
- University of Bath (GB)
- Corresponding author
- Garden, Jennifer A.
- Venue
- Catalysis Science & Technology
- Publisher
- Royal Society of Chemistry (RSC)
- Published
- 2022
- Volume
- 12
- Issue
- 4
- Pages
- 1070-1079
- ISSN
- 2044-4753 (ISSN-L)
- 2044-4761
- OpenAlex
- W3211394869
- Cited by
- 24
- References
- 46
- Citations by year
- 2026: 2 · 2025: 7 · 2024: 5 · 2023: 3 · 2022: 7
- FWCI
- 0.98
- Type
- journal article
- Language
- en
- Open access
- hybrid
- doi.org
- Licence
- Locations
- Catalysis Science & Technology (publishedVersion, cc-by)
- Edinburgh Research Explorer (University of Edinburgh) (submittedVersion, cc-by)
- Funders
- UK Research and Innovation (MR/T042710/1)
- Royal Society (RSG\R1\180101, UF\160021)
- Engineering and Physical Sciences Research Council (EP\L016419\1)
- L'Oreal USA (L’Oréal-UNESCO UK and Ireland Fellowship For Women in Science)
- United Nations Educational, Scientific and Cultural Organization (L’Oréal-UNESCO UK and Ireland Fellowship For Women in Science)
- Topics
- Physical Sciences › Materials Science › Biomaterials › biodegradable polymer synthesis and properties
- Physical Sciences › Chemical Engineering › Process Chemistry and Technology › Carbon dioxide utilization in catalysis
- Physical Sciences › Chemistry › Organic Chemistry › Asymmetric Synthesis and Catalysis
- Keywords
- heterobimetallic catalysts, lactide polymerization, Lewis acidity
About these checks
Registry, retraction, Cites and statistics results are computed, not judged, with one exception: a printed reference that no index lists is read once by a model before it counts as a citation error. Claims are extracted by a model and kept only when their quote appears verbatim in the text; each cited source is then checked, with a model’s help, for whether it says what the claim relies on. Those verdicts can be wrong — read the claim’s quote and the cited source before relying on one.
Statistics and arithmetic are recomputed, not judged.
Confidence bands are shown only for fields calibrated on our annotated test set. None is calibrated yet, so no band is shown.
What counts as a claim ›How we measure confidence ›How we check this ›
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