Institute of Chemical Research of Catalonia (ICIQ), Av. Països Catalans 16, 43007 Tarragona (Spain), Fax: (+34) 977-920-828.
Chemistry. 2014 Feb 17;20(8):2264-75. doi: 10.1002/chem.201302536. Epub 2014 Jan 20.
Al(III) complexes of amino-tris(phenolate) ligand scaffolds have been prepared to attain highly Lewis acidic catalysts. Combination of the aforementioned systems with ammonium halides provides highly active catalysts for the synthesis of organic carbonates through addition of carbon dioxide to oxiranes with initial turnover frequencies among the highest reported to date within the context of cyclic carbonate formation. Density functional theory (DFT) studies combined with kinetic data provides a rational for the relative high activity found for these Al(III) complexes, and the data are consistent with a monometallic mechanism. The activity and versatility of these Al(III) complexes has also been evaluated against some state-of-the-art catalysts and the combined results compare favorably in terms of catalyst construction, stability, activity, and applicability.
已制备了氨基三(苯氧)配体支架的 Al(III) 配合物,以获得高路易斯酸性催化剂。将上述系统与卤化铵结合,为通过将二氧化碳添加到环氧化物中合成有机碳酸酯提供了高活性催化剂,其初始周转率频率在迄今为止报道的环状碳酸酯形成背景下是最高的。密度泛函理论 (DFT) 研究与动力学数据相结合,为这些 Al(III) 配合物的相对高活性提供了合理的依据,并且数据与单金属机理一致。这些 Al(III) 配合物的活性和多功能性也已针对一些最先进的催化剂进行了评估,并且综合结果在催化剂结构、稳定性、活性和适用性方面具有优势。