冠醚碗状化合物：通过4'-吡啶甲基取代的12-冠-4醚与Ag⁺离子自组装形成的金属环番。

Crown bowl: metallocyclophane by self-assembly of 4'-pyridylmethyl-armed 12-crown-4 ethers with Ag+ ions.

作者信息

Habata Yoichi, Yamada Sachiko, Osaka Futoshi

机构信息

Department of Chemistry, Faculty of Science, Toho University, 2-2-1 Miyama, Funabashi, Chiba 274-8510, Japan.

出版信息

Inorg Chem. 2006 Feb 6;45(3):987-91. doi: 10.1021/ic051047u.

DOI:10.1021/ic051047u

PMID:16441104

Abstract

New 3'-pyridylmethyl- and 4'-pyridylmethyl-armed monoaza-12-crown-4 ethers were prepared by the reductive amination of monoaza-12-crown-4 with the appropriate pyridinecarbaldehyde in the presence of NaBH(OAc)3. X-ray crystallography, cold electrospray ionization mass spectrometry, and 1H NMR titration experiments show that Ag+ complexes with 3'-pyridylmethyl- and 4'-pyridylmethyl-armed monoaza-12-crown-4 ethers are dimetallo[3.3]metacyclophane and trimetallo[3.3.3]paracyclophane, respectively (crown bowl). The structure of the metallocyclophanes can be controlled by the positions of the N atoms in the pyridine side arms and the ring size of the crown moiety.

摘要

通过在三乙酰氧基硼氢化钠存在下，单氮杂-12-冠-4与适当的吡啶甲醛进行还原胺化反应，制备了新型的3'-吡啶甲基和4'-吡啶甲基取代的单氮杂-12-冠-4醚。X射线晶体学、冷电喷雾电离质谱和1H NMR滴定实验表明，Ag+与3'-吡啶甲基和4'-吡啶甲基取代的单氮杂-12-冠-4醚形成的配合物分别为双金属[3.3]间环环烷和三金属[3.3.3]对环环烷（冠醚碗）。金属环烷的结构可以通过吡啶侧链中N原子的位置和冠醚部分的环大小来控制。