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Synthesis of isoreticular zinc(II)-phosphonocarboxylate frameworks and their application in the Friedel-Crafts benzylation reaction

机译:等孔网状锌(II)-膦酰基羧酸盐骨架的合成及其在Friedel-Crafts苄化反应中的应用

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摘要

Three isoreticular zinc(II)-phosphonocarboxylate frameworks, namely {[Zn_3(pbdc)_2]·2 H_3O}_n (ZnPC-2), {[Zn_3(pbdc)_2]·Hpd·H _3O·4 H_2O}_n (Hpd@ZnPC-2) and {[Co _(1.5)Zn_(1.5)(pbdc)_2]·2 H_3O} _n (CoZnPC-2) (H_4pbdc=5-phosphonobenzene-1,3-dicarboxylic acid, pd=pyrrolidine), were solvothermally synthesized. ZnPC-2 has a 3D structure based on trinuclear Zn~(II) clusters (Zn_3-SBU) showing 3D interconnected channels. Hpd@ZnPC-2 contains an isoreticular framework of ZnPC-2 with small channels blocked by Hpd molecules. In CoZnPC-2, Zn~(II) ions in ZnPC-2 are partially substituted by Co~(II) ions. The Friedel-Crafts benzylation reactions were carried out over these isoreticular porous materials. The catalytic results reveal that ZnPC-2 is an excellent heterogeneous Lewis acid catalyst with a high selectivity (>90 %) towards less bulky para-oriented products. The catalytic reaction has been proved to occur inside the pore of ZnPC-2, and the immobilized Zn _3-SBUs are the active sites.
机译:三个等网状锌(II)-膦酰基羧酸盐骨架,即{[Zn_3(pbdc)_2]·2 H_3O} _n(ZnPC-2),{[Zn_3(pbdc)_2]·Hpd·H _3O·4 H_2O} _n(Hpd @ ZnPC-2)和{[Co _(1.5)Zn_(1.5)(pbdc)_2]·2 H_3O} _n(CoZnPC-2)(H_4pbdc = 5-膦酰基苯-1,3-二羧酸,pd =吡咯烷) ,被溶剂热合成。 ZnPC-2具有基于显示3D互连通道的三核Zn〜(II)簇(Zn_3-SBU)的3D结构。 Hpd @ ZnPC-2包含ZnPC-2的同网状骨架,小通道被Hpd分子阻断。在CoZnPC-2中,ZnPC-2中的Zn〜(II)离子被Co〜(II)离子部分取代。在这些等网状多孔材料上进行Friedel-Crafts苄基化反应。催化结果表明,ZnPC-2是一种出色的多相路易斯酸催化剂,对体积较小的对位产物具有较高的选择性(> 90%)。已证明催化反应发生在ZnPC-2的孔内,固定化的Zn _3-SBUs是活性位点。

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