Dipartimento di Chimica e Biologia "Adolfo Zambelli", Università di Salerno, Via Giovanni Paolo II, 132-84084, Fisciano (SA), Italia.
Dipartimento di Chimica, Biologia e Biotecnologie, Università degli Studi di Perugia, Via Elce di Sotto, 8-06123, Perugia, Italia.
Angew Chem Int Ed Engl. 2017 Nov 6;56(45):14227-14231. doi: 10.1002/anie.201707194. Epub 2017 Oct 6.
The solution structure of AlMe F and its reactivity with a prototypical ansa-metallocene have been investigated by advanced NMR techniques, in an attempt to indirectly shed some light on the structure and working principles of methylalumoxane (MAO) mixtures in olefin polymerization. In solution, AlMe F gives rise to a complex equilibrium of oligomeric species, including a heterocubane [(Me Al) F ] tetramer, resembling the behavior of MAO. This complex mixture reacts with (ETH)ZrMe (ETH=rac-[ethylenebis(4,5,6,7-tetrahydro-1-indenyl)]) to afford [(ETH)ZrMe (μ-F)(AlMe F) AlMe ] inner-sphere ion pairs through successive insertions/deinsertions of AlMe F units into the Zr⋅⋅⋅(μ-F) bond.
采用先进的 NMR 技术研究了 AlMe F 的溶液结构及其与典型的ansa-茂金属络合物的反应性，试图间接地阐明甲基铝氧烷 (MAO) 混合物在烯烃聚合中的结构和工作原理。在溶液中，AlMe F 产生了复杂的低聚物种平衡，包括类似于 MAO 行为的杂棱烷 [(Me Al) F ] 四聚体。这种复杂的混合物与 (ETH)ZrMe（ETH=rac-[ethylenebis(4,5,6,7-tetrahydro-1-indenyl)]) 反应，通过 AlMe F 单元连续插入/脱插入 Zr⋅⋅⋅(μ-F) 键，生成 [(ETH)ZrMe(μ-F)(AlMe F)AlMe ] 内球离子对。
