Romain Charles, Garden Jennifer A, Trott Gemma, Buchard Antoine, White Andrew J P, Williams Charlotte K
Department of Chemistry, Imperial College London, London, SW7 2AZ, UK.
EastCHEM School of Chemistry, University of Edinburgh, Edinburgh, EH9 3FJ, UK.
Chemistry. 2017 May 29;23(30):7367-7376. doi: 10.1002/chem.201701013. Epub 2017 May 5.
Two new di-zinc-aryl complexes, [LZn Ph ] and [LZn (C F ) ], coordinated by a diphenol tetraamine macrocyclic ligand have been prepared and fully characterised, including by single-crystal X-ray diffraction experiments. The complexes' reactivities with monomers including carbon dioxide, cyclohexene oxide, phthalic anhydride, isopropanol and phenol were investigated using both experimental studies and density functional theory calculations. In particular, [LZn Ph ] readily inserts carbon dioxide to form a carboxylate, at 1 bar pressure, whereas [LZn (C F ) ] does not react. Under these conditions [LZn Ph ] shows moderate activity in the ring-opening copolymerisation of cyclohexene oxide/carbon dioxide (TOF=20 h ), cyclohexene oxide/phthalic anhydride (TOF=33 h ) and the ring-opening polymerisations of rac-lactide (TOF=99 h ) and ϵ-caprolactone (TOF=5280 h ).
通过二酚四胺大环配体配位的两种新型二锌芳基配合物[LZnPh]和[LZn(C6F5)]已被制备并进行了全面表征，包括通过单晶X射线衍射实验。使用实验研究和密度泛函理论计算研究了这些配合物与包括二氧化碳、环氧环己烷、邻苯二甲酸酐、异丙醇和苯酚在内的单体的反应活性。特别地，[LZnPh]在1巴压力下能轻易插入二氧化碳形成羧酸盐，而[LZn(C6F5)]不发生反应。在这些条件下，[LZnPh]在环氧环己烷/二氧化碳的开环共聚（TOF = 20 h⁻¹）、环氧环己烷/邻苯二甲酸酐的开环共聚（TOF = 33 h⁻¹）以及外消旋丙交酯的开环聚合（TOF = 99 h⁻¹）和ε-己内酯的开环聚合（TOF = 5280 h⁻¹）中表现出中等活性。
