双功能铝配合物催化环状碳酸酯合成中反离子的影响。
Influence of the Counterion on the Synthesis of Cyclic Carbonates Catalyzed by Bifunctional Aluminum Complexes.
机构信息
Departamento de Química Inorgánica, Orgánica y Bioquímica-Centro de Innovación en Química Avanzada (ORFEO-CINQA), Facultad de Ciencias y Tecnologías Químicas , Universidad de Castilla-La Mancha , 13071 Ciudad Real , Spain.
Laboratorio de Química Inorgánica, Facultad de Química , Universidad Católica de Chile , Casilla 306 , Santiago-22 6094411 , Chile.
出版信息
Inorg Chem. 2019 Mar 4;58(5):3396-3408. doi: 10.1021/acs.inorgchem.8b03475. Epub 2019 Feb 8.
New bifunctional aluminum complexes have been prepared with the aim of studying the effect of a counterion on the synthesis of cyclic carbonates from epoxides and carbon dioxide (CO). Neutral ligand 1 was used as a precursor to obtain four novel mesylate, chloride, bromide, and iodide zwitterionic NNO ligands (2-5). The reaction of these ligands with 1 or 2 equiv of AlR (R = Me, Et) allowed the synthesis of mono- and bimetallic bifunctional aluminum complexes [AlR(κ-mbpzappe)]X [X = Cl, R = Me (6), Et (7); X = Br, R = Me (8), Et (9); X = I, R = Me (10), Et (11)] and [{AlR(κ-mbpzappe)}(μ-O){AlR}]X [X = MeSO, R = Me (12), Et (13); X = Cl, R = Me (14), Et (15); X = Br, R = Me (16), Et (17); X = I, R = Me (18), Et (19)] via alkane elimination. These complexes were studied as catalysts for the synthesis of cyclic carbonates from epoxides and CO. Iodide complex 11 showed to be the most active catalyst for terminal epoxides, whereas bromide complex 9 was found to be the optimal catalyst when internal epoxides were used, showing the importance of the nucleophile cocatalyst on the catalytic activity.
已经制备了新的双功能铝配合物，目的是研究抗衡离子对环氧乙烷和二氧化碳（CO）合成环状碳酸酯的影响。中性配体 1 被用作前体，以获得四个新型甲磺酸酯、氯化物、溴化物和碘化物两性离子 NNO 配体（2-5）。这些配体与 1 或 2 当量的 AlR（R = Me，Et）反应，允许合成单和双功能双功能铝配合物[AlR（κ-mbpzappe）]X [X = Cl，R = Me（6），Et（7）; X = Br，R = Me（8），Et（9）; X = I，R = Me（10），Et（11）]和[{AlR（κ-mbpzappe）}（μ-O）{AlR}]X [X = MeSO，R = Me（12），Et（13）; X = Cl，R = Me（14），Et（15）; X = Br，R = Me（16），Et（17）; X = I，R = Me（18），Et（19）]通过烷烃消除。这些配合物被研究为环氧乙烷和 CO 合成环状碳酸酯的催化剂。碘化物配合物 11 被证明是末端环氧化物最有效的催化剂，而当使用内部环氧化物时，溴化物配合物 9 被发现是最佳催化剂，这表明亲核助催化剂对催化活性的重要性。
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