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Mononuclear complexes of a tridentate redox-active ligand with sulfonamido groups: structure, properties, and reactivity†
Chemical Science ( IF 7.6 ) Pub Date : 2018-07-02 00:00:00 , DOI: 10.1039/c7sc05445a Sarah A Cook 1 , Justin A Bogart 1 , Noam Levi 1 , Andrew C Weitz 2 , Curtis Moore 3 , Arnold L Rheingold 3 , Joseph W Ziller 1 , Michael P Hendrich 2 , A S Borovik 1
Chemical Science ( IF 7.6 ) Pub Date : 2018-07-02 00:00:00 , DOI: 10.1039/c7sc05445a Sarah A Cook 1 , Justin A Bogart 1 , Noam Levi 1 , Andrew C Weitz 2 , Curtis Moore 3 , Arnold L Rheingold 3 , Joseph W Ziller 1 , Michael P Hendrich 2 , A S Borovik 1
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The design of molecular complexes of earth-abundant first-row transition metals that can catalyze multi-electron C–H bond activation processes is of interest for achieving efficient, low-cost syntheses of target molecules. To overcome the propensity of these metals to perform single-electron processes, redox-active ligands have been utilized to provide additional electron equivalents. Herein, we report the synthesis of a novel redox active ligand, [ibaps]3−, which binds to transition metals such as FeII and CoII in a meridional fashion through the three anionic nitrogen atoms and provides additional coordination sites for other ligands. In this study, the neutral bidentate ligand 2,2′-bipyridine (bpy) was used to complete the coordination spheres of the metal ions and form NEt4[MII(ibaps)bpy] (M = Fe (1) or Co (1-Co)) salts. The FeII salt exhibited rich electrochemical properties and could be chemically oxidized by 1 and 2 equiv. of ferrocenium to form singly and doubly oxidized species, respectively. The reactivity of 1 towards intramolecular C–H bond amination of aryl azides at benzylic and aliphatic carbon centers was explored, and moderate to good yields of the resulting indoline products were obtained.
中文翻译：
三齿氧化还原活性配体与磺酰胺基团的单核配合物：结构、性质和反应性†
地球上丰富的第一行过渡金属分子配合物的设计可以催化多电子C-H键活化过程，对于实现目标分子的高效、低成本合成具有重要意义。为了克服这些金属进行单电子过程的倾向，氧化还原活性配体被用来提供额外的电子当量。在此，我们报道了一种新型氧化还原活性配体 [ibaps] 3−的合成，它通过三个阴离子氮原子以子午方式与Fe II和 Co II等过渡金属结合，并为其他配体提供额外的配位位点。本研究采用中性二齿配体2,2′-联吡啶(bpy)来完成金属离子的配位球并形成NEt 4 [ M II ( ibaps)bpy] (M = Fe ( 1 ) 或 Co ( 1 -Co))盐。Fe II盐表现出丰富的电化学性能，可以被1和2当量的化学氧化。二茂铁分别形成单氧化和双氧化物质。探索了1对芳基叠氮化物在苯甲基和脂肪族碳中心进行分子内 C-H 键胺化的反应性，并获得了中等至良好的二氢吲哚产物产率。
更新日期：2018-07-02
中文翻译：
三齿氧化还原活性配体与磺酰胺基团的单核配合物：结构、性质和反应性†
地球上丰富的第一行过渡金属分子配合物的设计可以催化多电子C-H键活化过程，对于实现目标分子的高效、低成本合成具有重要意义。为了克服这些金属进行单电子过程的倾向，氧化还原活性配体被用来提供额外的电子当量。在此，我们报道了一种新型氧化还原活性配体 [ibaps] 3−的合成，它通过三个阴离子氮原子以子午方式与Fe II和 Co II等过渡金属结合，并为其他配体提供额外的配位位点。本研究采用中性二齿配体2,2′-联吡啶(bpy)来完成金属离子的配位球并形成NEt 4 [ M II ( ibaps)bpy] (M = Fe ( 1 ) 或 Co ( 1 -Co))盐。Fe II盐表现出丰富的电化学性能，可以被1和2当量的化学氧化。二茂铁分别形成单氧化和双氧化物质。探索了1对芳基叠氮化物在苯甲基和脂肪族碳中心进行分子内 C-H 键胺化的反应性，并获得了中等至良好的二氢吲哚产物产率。
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