二茂钌共轭大环氮杂冠醚的合成及结构

合成并表征了质子化的N-(二茂钌基甲基)-1,4,7-三氮杂-9-冠-3(1)和N,N′,N″-三-(二茂钌基甲基)-1,4,7-三氮杂-9-冠-3(2).用X射线衍射法测定了化合物2的结构.化合物2的晶体属P₂₁/a空间群.晶胞参数a=1.4285(3)nm,b=1.9888(3)nm,c=1.9133(3)nm;β=109.12(2)°;V=5.1358(1.0)nm³;Z=4.D_c=1.665g/cm³.1和2的核磁共振谱表明,化合物中取代Cp环上质子的共振吸收较二茂钌Cp环上质子的吸收向低场移动.这表明质子化的1,4,7-三氮杂-9冠-3对Cp环上质子具有去屏蔽作用.化合物2的电位扫描曲线在0.84V处出现一个氧化波.

Synthesis and Structure of Ruthenocene-conjugated Microcyclic Triaza Crown Ether

Protonated N-(ruthenocenylmethyl)-1,4,7-triazacyclononane(1) and N, N′, N″-tris-(ruthenocenylmethyl)-1, 4, 7-triazacyclononane(2) were prepared and characterized. The structure of 2 was determined by X-ray crystallographic method. The crystal belongs to P2₁/a space group and cell parameters are a = 1.4285(3) nm, b = 1.9888(3) nm, c = 1.9133(3) nm; β = 109.12(2)°; V =5.1358(1.0) nm³; Z =4. D_c=1.665 g/cm³. ¹HNMR spectra of 1 and 2 revealed that the absorptions of the protons on substituted Cp rings in these compounds had a down-field shift from those of the protons on the Cp rings of ruthenocene. The observation suggests that the protonated 1,4,7-triazacyclononane has a deshielding effect on the protons of the ruthenocene units. The CV curve of 2 gave an oxidation wave at 0.84 V.