The synthesis and characterization of a bidentate complex of 1,1′-(1,3-phenylene)bis(3-butylimidazolium) pincer proligand with molybdenum – A non-pincer binding mode
The synthesis and characterization of a bidentate complex of 1,1′-(1,3-phenylene)bis(3-butylimidazolium) pincer proligand with molybdenum – A non-pincer binding mode
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1,1-(1,3-亚苯基)双(3-丁基咪唑鎓)钳配体与钼的双齿复合物的合成和表征 — 非钳结合模式
DOI：
10.1016/j.poly.2023.116714
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发表时间：
2024
期刊：
影响因子：
2.6
通讯作者：
Hollis, T. Keith
中科院分区：
文献类型：
--
作者：
Juárez-Escamilla, Samuel D.;Dey, Sriloy;Donnadieu, Bruno;Hollis, T. Keith
采用先金属化再金属转移的方法合成了双齿钼配合物四氯[6-（3′-丁基咪唑-1 ′-基）-2-（3″-丁基咪唑-1 ″-基-2 ″-亚甲基-κC2）苯基-κC1]钼（IV）3。DCM与HNMe 2反应生成酸性铵离子，使双齿配合物质子化，从而形成双齿配合物。通过优化合成工艺，得到了高产率的四氯[6-（3′-丁基咪唑-1 ′-基）-2-（3″-丁基咪唑-1 ″-基-2 ″-亚甲基-κC2）苯基-κC1]钼（IV）配合物。本文报道了双齿配合物3的晶体结构。尝试避免使用不同溶剂或起始材料的酸性反应条件，产生基于MS分析的双连接的Mo络合物双[2，6-双（3′-丁基咪唑-1 ′-基-2 ′-亚甲基-κC2）苯基-κC1]二氯化钼（IV）。电子和协调的不饱和度，在所得的双齿复合物，3，打开新的可能性，协调传入基板，同时也允许通过氧化加成的钳状基序。获得NHC到/从咪唑鎓的互变开辟了非无辜配体途径的新途径，用于在诸如氮还原为氨的反应中进行质子穿梭。
The synthesis of the bidentate Mo complex tetrachlorido[6-(3′-butylimidazolium-1′-yl)-2-(3″-butylimidazol-1″-yl-2″-idene-κC2)phenyl-κC1]molybdenum(IV)3was carried out using the metalation followed by transmetalation methodology. The transmetalation process led to a bidentate complex after the reaction of DCM with HNMe2formed an acidic ammonium ion that protonated the bidentate complex. Optimization of the synthetic methodology provided the tetrachlorido[6-(3′-butylimidazolium-1′-yl)-2-(3″-butylimidazol-1″-yl-2″-idene-κC2)phenyl-κC1]molybdenum(IV) complex in high yield. The crystal structure of the bidentate complex,3, is reported herein. Attempts to avoid the acidic reaction conditions with different solvents or starting materials produced the bis-ligated Mo complex bis[2,6-bis(3′-butylimidazol-1′-yl-2′-idene-κC2)phenyl-κC1]molybdenum(IV) dichloride based on MS analysis. Electronic and coordinative unsaturation in the resulting bidentate complex,3, open new possibilities for coordination of incoming substrates while also allowing access to the pincer-like motif via oxidative addition. Access to the interconversion of a NHC to/from imidazolium opens new avenues of non-innocent ligand pathways for proton shuttling in reactions such as nitrogen reduction to ammonia.