Synthesis, Structure, and Electrochemical Property of a Bimetallic Bis-2-pyridylidene Palladium Acetate Complex
Synthesis, Structure, and Electrochemical Property of a Bimetallic Bis-2-pyridylidene Palladium Acetate Complex
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DOI：
10.1246/cl.170091
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发表时间：
2017-02
影响因子：
1.6
通讯作者：
Tetsushi Yoshidomi;Tomohiro Fukushima;K. Itami;Yasutomo Segawa
中科院分区：
文献类型：
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作者：
Tetsushi Yoshidomi;Tomohiro Fukushima;K. Itami;Yasutomo Segawa
合成了一种双乙酸根桥联的（双-2-吡啶亚甲基）钯（II）配合物，并利用循环伏安法研究了其氧化行为。密度泛函理论计算结果表明，双-2-吡啶亚基具有较强的电子给体能力和较高的平面性，是一种潜在的稳定双金属Pd（III）的有效配体.通过C-H硼化和Suzuki-Miyaura交叉偶联反应合成了二叔丁基苯基取代的（双-2-吡啶亚基）Pd（II）碳酸盐配合物，并成功地将其转化为乙酸根桥联的Pd（II）碳酸盐配合物。乙酸根桥联的（双-2-吡啶亚基）Pd（II）配合物的结构参数和氧化电位表明，与中性双齿配体相比，双-2-吡啶亚基配体具有较强的给电子能力.尽管有几次尝试，（双-2-吡啶亚基）钯（III）配合物不能被分离，因为它们的不稳定性。
A bimetallic acetate-bridged (bis-2-pyridylidene)Pd(II) complex was synthesized and its oxidation behavior was investigated by cyclic voltammetry. The density functional theory calculation indicated that bis-2-pyridylidene is a potentially useful ligand to stabilize bimetallic Pd(III) species owing to its strong electron donation ability and high planarity. The di-tert-butylphenyl-substituted (bis-2-pyridylidene)Pd(II) carbonate complex was synthesized via sequential C–H borylation and Suzuki–Miyaura cross-coupling reactions, and the carbonate complex was successfully converted into an acetate-bridged bimetallic complex. The structural parameters and oxidation potentials of the acetate-bridged (bis-2-pyridylidene)Pd(II) complex indicated the strong electron donation ability of the bis-2-pyridylidene ligand compared with neutral bidentate ligands. Despite several attempts, (bis-2-pyridylidene)Pd(III) complexes could not be isolated because of their instability.