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Heterodinuclear complexes featuring Zn(ii) and M = Al(iii), Ga(iii) or In(iii) for cyclohexene oxide and CO2 copolymerisation | |
Dalton Transactions | |
2019-12-09 | |
出版年 | 2019 |
国家 | 英国 |
领域 | 地球科学 ; 资源环境 |
英文摘要 | Arron C. Deacy, Christopher B. Durra and Charlotte K. Williams https://doi.org/10.1039/C9DT02918D The ring opening copolymerisation of CO2 and epoxides is a useful means to valorise waste emissions and to reduce pollution in polymer manufacturing. Heterodinuclear catalysts, particularly those of Zn(II)/Mg(II), have shown better performances than homodinuclear analogues in this reaction. As part of on-going efforts to better understand the catalytic synergy, this work describes a series of heterodinuclear complexes, combining Zn(II) with a metal from Group 13 (M = Al(III), Ga(III) or In(III)). The complexes are synthesised from a symmetrical macrocyclic ligand in high yields via sequential metalation steps and are the thermodynamic reaction products. The Zn(II)/Group 13 complexes are effective homogeneous catalysts for the ring opening copolymerisation (ROCOP) of cyclohexene oxide at 1 bar pressure of carbon dioxide, but all show inferior performances compared to the di-zinc analogue. The CO2 uptake into the polymer increases in the order Al(III) < Ga(III) < In(III) which is attributed to lower Lewis acidity heavier Group 13 homologues showing a reduced tendency to form ether linkages. Concurrently, polycarbonate activity increases down the Group 13 series consistent with weaker metal–oxygen bonds which show enhanced lability to insertion reactions. |
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来源平台 | Oxford Martin School, University of Oxford |
文献类型 | 科技报告 |
条目标识符 | http://119.78.100.173/C666/handle/2XK7JSWQ/270780 |
专题 | 地球科学 资源环境科学 |
推荐引用方式 GB/T 7714 | Dalton Transactions. Heterodinuclear complexes featuring Zn(ii) and M = Al(iii), Ga(iii) or In(iii) for cyclohexene oxide and CO2 copolymerisation,2019. |
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