Issue 15, 2019

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

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

Supplementary files

Article information

Article type
Paper
Submitted
08 Febr. 2019
Accepted
12 Marts 2019
First published
21 Marts 2019
This article is Open Access
Creative Commons BY license

Dalton Trans., 2019,48, 4887-4893

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

This article is licensed under a Creative Commons Attribution 3.0 Unported Licence. You can use material from this article in other publications without requesting further permissions from the RSC, provided that the correct acknowledgement is given.

Read more about how to correctly acknowledge RSC content.

Social activity

Spotlight

Advertisements