Synthesis of a Redox-Active NNP-Type Pincer Ligand and Its Application to Electrocatalytic CO2 Reduction With First-Row Transition Metal Complexes
Synthesis of a Redox-Active NNP-Type Pincer Ligand and Its Application to Electrocatalytic CO2 Reduction With First-Row Transition Metal Complexes
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DOI：
10.3389/fchem.2019.00330
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发表时间：
2019-05
影响因子：
5.5
通讯作者：
Kallol Talukdar;Asala Issa;J. W. Jurss
中科院分区：
文献类型：
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作者：
Kallol Talukdar;Asala Issa;J. W. Jurss
我们报道了一种刚性膦取代的、具有氧化还原活性的钳形配体的合成及其在第一行过渡金属配合物电催化CO2还原中的应用。通过2，8-二溴喹啉和2-（三丁基甲锡烷基）吡啶的Stille偶联，然后通过钯催化的与HPPh 2的交叉偶联制备三齿配体。从各种金属前体合成配合物，并通过NMR，高分辨率质谱，元素分析和循环伏安法进行表征。双螯合金属络合物，而不是单螯合络合物的形成，有利于在所有的合成条件下探索。络合物进行了评估，其介导电催化CO2还原的能力，其中钴络合物被发现具有最好的活性，在水作为添加的质子源的存在下，CO2到CO的转化。
We report the synthesis of a rigid phosphine-substituted, redox-active pincer ligand and its application to electrocatalytic CO2 reduction with first-row transition metal complexes. The tridentate ligand was prepared by Stille coupling of 2,8-dibromoquinoline and 2-(tributylstannyl)pyridine, followed by a palladium-catalyzed cross-coupling with HPPh2. Complexes were synthesized from a variety of metal precursors and characterized by NMR, high-resolution mass spectrometry, elemental analysis, and cyclic voltammetry. Formation of bis-chelated metal complexes, rather than mono-chelated complexes, was favored in all synthetic conditions explored. The complexes were assessed for their ability to mediate electrocatalytic CO2 reduction, where the cobalt complex was found to have the best activity for CO2-to-CO conversion in the presence of water as an added proton source.