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Issue 15, 2019
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Polynuclear alkoxy–zinc complexes of bowl-shaped macrocycles and their use in the copolymerisation of cyclohexene oxide and CO2

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Abstract

The reactions between alcohols and the tetranuclear ethyl–Zn complexes of an ortho-phenylene-bridged polypyrrole macrocycle, Zn4Et4(L1) 1 and the related anthracenyl-bridged macrocyclic complex, Zn4Et4(THF)4(L2) 2 have been studied. With long-chain alcohols such as n-hexanol, the clean formation of the tetranuclear hexoxide complex Zn4(OC6H13)4(L1) 3 occurs. In contrast, the use of shorter-chain alcohols such as i-propanol results in the trinuclear complex Zn32-OiPr)23-OiPr)(HL1) 4 that arises from demetalation; this complex was characterised by X-ray crystallography. The clean formation of these polynuclear zinc clusters allowed a study of their use as catalysts in the ring-opening copolymerisation (ROCOP) reaction between cyclohexene oxide and CO2. In situ reactions involving the pre-catalyst 1 and n-hexanol formed the desired polymer with the best selectivity for polycarbonate (90%) at 30 atm CO2, whilst the activity and performance of pre-catalyst 2 was poor in comparison.

Graphical abstract: Polynuclear alkoxy–zinc complexes of bowl-shaped macrocycles and their use in the copolymerisation of cyclohexene oxide and CO2

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Article information


Submitted
08 Feb 2019
Accepted
12 Mar 2019
First published
21 Mar 2019

This article is Open Access

Dalton Trans., 2019,48, 4887-4893
Article type
Paper

Polynuclear alkoxy–zinc complexes of bowl-shaped macrocycles and their use in the copolymerisation of cyclohexene oxide and CO2

J. R. Pankhurst, S. Paul, Y. Zhu, C. K. Williams and J. B. Love, Dalton Trans., 2019, 48, 4887
DOI: 10.1039/C9DT00595A

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