Azo-triazolide bis-cyclometalated Ir(iii) complexes via cyclization of 3-cyanodiarylformazanate ligands.
Azo-triazolide bis-cyclometalated Ir(iii) complexes via cyclization of 3-cyanodiarylformazanate ligands.
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DOI：
10.1039/c9dt03914g
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发表时间：
2019-11
影响因子：
4
通讯作者：
Ge Mu;Zhili Wen;J. Wu;Thomas S. Teets
中科院分区：
文献类型：
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作者：
Ge Mu;Zhili Wen;J. Wu;Thomas S. Teets
在这项工作中，我们描述了空间阻碍的 1,5-二芳基-3-氰基甲氮酸双环金属化铱 (iii) 配合物的合成，其中两个配合物在反应过程中经历氧化还原中性环化，产生碳键合的 2-芳基-4-芳基偶氮基-2H-1,2,3-三唑化物配体。这种转化提供了一种获得 2-芳基-4-芳基偶氮基-2H-1,2,3-三唑化物配体（一类迄今为止未报道的螯合配体）的方法。通过单晶 X 射线衍射对一种甲酸酯络合物和两种三唑化物络合物进行了结构表征，红外光谱是区分甲臜酸酯和三唑化物结构的主要本体技术。所有配合物均通过紫外-可见吸收光谱和循环伏安法进一步表征，其中三唑化合物具有与甲酸盐配合物相似的前沿轨道能量，但可见光吸收要少得多。
In this work we describe the synthesis of sterically encumbered 1,5-diaryl-3-cyanoformazanate bis-cyclometalated iridium(iii) complexes, two of which undergo redox-neutral cyclization during the reaction to produce carbon-bound 2-aryl-4-arylazo-2H-1,2,3-triazolide ligands. This transformation offers a method for accessing 2-aryl-4-arylazo-2H-1,2,3-triazolide ligands, a heretofore unreported class of chelating ligands. One formazanate complex and both triazolide complexes are structurally characterized by single-crystal X-ray diffraction, with infrared spectroscopy being the primary bulk technique to distinguish the formazanate and triazolide structures. All complexes are further characterized by UV-Vis absorption spectroscopy and cyclic voltammetry, with the triazolide compounds having similar frontier orbital energies to the formazanate complexes but much less visible absorption.