One-Pot Conditional Self-Assembly of Multicopper Metallacycles
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- 作者：Kom-Bei Shiu ; Shih-An Liu ; Gene-Hsiang Lee
- 刊名：Inorganic Chemistry
- 出版年：2010
- 出版时间：November 1, 2010
- 年：2010
- 卷：49
- 期：21
- 页码：9902-9908
- 全文大小：1006K
- 年卷期：v.49,no.21(November 1, 2010)
- ISSN：1520-510X
文摘
The self-assembly of supramolecular metallacycles via the coordination-driven directional bonding approach can be modified to produce some unexpected structural variations. The combination of a flexible ligand-capped dinuclear transition-metal acceptor like [Cu2(dppm)2(NCMe)2]X2 (1X2; dppm = Ph2PCH2PPh2; X− = BF4−, PF6−, or BPh4−) with monodentate−bidentate donors like 2-, 3-, and 4-pyridylcarboxylates produced oligomeric compounds [{Cu2(dppm)2}(μ-(2-PyCO2))]2X2 (2X2), [{Cu2(dppm)2}(μ-(3-PyCO2))]2X2 (3X2), and [{Cu2(dppm)2}(μ-(4-PyCO2))]4X4 (4X4), respectively, as the thermodynamically stable products in one-pot reactions. However, the modified self-assembly is still subject to steric hindrance. The reaction of complex 1(BF4)2 with 6-Me-3-PyCO2H did not produce a polygonal dimeric metallacycle but a simple dinuclear complex, [Cu2(dppm)2(6-Me-3-PyCO2)](BF4) (5(BF4)). The crystal structures of complexes 2(PF6)2, 3(PF6)2, 4(BF4)4, and 5(BF4) were determined using X-ray diffraction.