Journal
DALTON TRANSACTIONS
Volume 48, Issue 15, Pages 4887-4893Publisher
ROYAL SOC CHEMISTRY
DOI: 10.1039/c9dt00595a
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Funding
- University of Edinburgh
- EPSRC [EP/L017393/1, EP/K014668/1]
- Chinese Scholarship Council
- Principal's Career Development Scholarship Scheme
- EPSRC [EP/L017393/1, EP/K014668/1] Funding Source: UKRI
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The reactions between alcohols and the tetranuclear ethyl-Zn complexes of an ortho-phenylene-bridged polypyrrole macrocycle, Zn4Et4(L-1) 1 and the related anthracenyl-bridged macrocyclic complex, Zn4Et4(THF)(4)(L-2) 2 have been studied. With long-chain alcohols such as n-hexanol, the clean formation of the tetranuclear hexoxide complex Zn-4(OC6H13)(4)(L-1) 3 occurs. In contrast, the use of shorter-chain alcohols such as i-propanol results in the trinuclear complex Zn-3((2)-(OPr)-Pr-i)(2)((3)-(OPr)-Pr-i)(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.
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