Four N,O‐bidentate chelating ligands [L¹=N‐(4‐thiazolylmethyl)morpholine‐N‐oxide, L²=N‐(2‐pyridylmethyl)pyrrolidine‐N‐oxide, L³=N‐(4‐thiazolylmethyl)pyrrolidine‐N‐oxide, and L⁴=N‐(2‐pyridylmethyl)morpholine‐N‐oxide] were designed and synthesized. The treatment of N,O‐bidentate ligands with CuCl₂ in ethanol at room temperature afforded four new copper complexes—[Cu(L¹)₂]Cl₂ (I), [Cu(L²)₂][CuCl₄] (II), [Cu(L³)₂Cl]₂[CuCl₂(H₂O)₂]Cl₂⋅10 H₂O (III) and [Cu(L⁴)₂][Cu(L⁴)₂(CH₃OH)₂][CuCl₄]₂ (IV)—which were fully characterized by single‐crystal X‐ray diffraction, IR spectroscopy and elemental analyses. Most interestingly, the single‐crystal X‐ray diffraction analyses revealed that the N,O‐bidentate ligands L¹–L⁴ can tune the corresponding geometry configuration of copper atoms in complexes I–IV. The copper atoms in I and II showed four‐coordinated distorted square planar geometry, whereas the central copper atom in III adopted a distorted square pyramidal geometry. It should be noted that complex IV was constructed by a distorted square planar CuN₂O₂ unit, one octahedral CuN₂O₄ unit and two [CuCl₄]²⁻ anions. Importantly, these copper(II) complexes, especially complex IV, showed high catalytic activity in Chan–Lam coupling reactions of primary or secondary amines with arylboronic acid under mild conditions. Substrates with many functional groups were tolerated and the C–N coupling products were afforded in good to excellent yields (up to 96 % yield).

中文翻译：

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四种N，O-二齿螯合的可调谐铜（II）配合物：Chan-Lam偶联反应的合成，结构表征和出色的催化性能

四个N，O-双齿螯合配体[ L ¹ = N-（4-噻唑基甲基）吗啉-N-氧化物，L ² = N-（2-吡啶基甲基）吡咯烷-N-氧化物，L ³ = N-（4-噻唑基甲基）吡咯烷-N-氧化物，L ⁴ = N-（2-吡啶基甲基）吗啉-N-氧化物]的设计和合成。在室温下用CuCl ₂在乙醇中处理N，O-双齿配体，得到了四个新的铜配合物-[Cu（L ¹）₂ ] Cl ₂（我），[Cu（上大号²）₂ ] [的CuCl ₄ ]（II），[Cu（上大号³）₂ CL] ₂ [的CuCl ₂（H ₂ O）₂ ]氯₂ ⋅ 10 H ₂ O（III）和[Cu（L ⁴）₂ ] [Cu（L ⁴）₂（CH ₃ OH）₂ ] [CuCl ₄ ] ₂（IV）—通过单晶X射线衍射，红外光谱和元素分析充分表征。最有趣的是，单晶X射线衍射分析表明，N，O形的配体L ¹ - L ⁴可以调节配合物I - IV中铜原子的相应几何构型。I和II中的铜原子显示出四坐标畸变的正方形平面几何形状，而III中的中心铜原子采用了畸变的正方形锥体几何形状。应该注意的是，复合物 IV是由扭曲的方形CuN ₂ O _{2构成的。}单元，一个八面体CuN ₂ O ₄单元和两个[CuCl ₄ ] ^2-阴离子。重要的是，这些铜（II）配合物，尤其是IV配合物， 在温和条件下，伯胺或仲胺与芳基硼酸的Chan-Lam偶联反应显示出高催化活性。具有许多官能团的底物是可以耐受的，并且提供了C–N偶联产物，具有良好至优异的产率（高达96％的产率）。