(C_5H_(11)N_2)~+和(C_7H_(12)N_2)~(2+)的NMR研究

结合1H NMR,13C NMR谱,分别对钨、钼配合物{WO2(C10H6O2)2(C5H11N2)2H2N(CH2)3NH2]}3(1),{(C5H11N2)2H2N(CH2)3NH2]MoO2(C10H6O2)2]}(2),{(C7H12N2)2MoO2(C10H8O2)2]}(3)晶体结构中小分子环进行了归属.其中,配合物1和2中(C5H11N2)+的NMR研究证实了六元环由1,3-丙二胺和乙腈化合而成,配合物3中(C7H12N2)2+的NMR谱图证实了七元环由乙二胺和乙酰丙酮化合而成,并且推导出这些亲核加成-消除反应的反应机理.配合物1~3中的小分子环的合成在其它体系中尚未见报导,而在合成它们的反应中作为新产物随主体晶体析出,并由晶体结构解析和NMR得到了证实.

An NMR Studies of (C5H11N2)+ and (C7H12N2)2+

The structure of small molecular rings (C₅H₁₁N₂)+ and (C₇H₁₂N₂)²⁺ in tungstate and molybdate complexes {WO₂(C₁₀H₆O₂)₂(C₅H₁₁N₂)₂H₂N(CH₂)₃NH₂]}₃ (1), {(C₅H₁₁N₂)₂H₂N(CH₂)₃NH₂]MoO₂(C₁₀H₆O₂)₂]} (2) and {(C₇H₁₂N₂)₂MoO₂(C₁₀H₈O₂)₂]} (3) were studied by ¹H and ¹³C NMR. The NMR data of (C₅H₁1N₂)⁺ in complexes 1 and 2 indicated the existence of two six-membered rings, which are composed of 1,3-diaminopropane and acetonitrile. The NMR spectra of (C7H12N2)²⁺ in complex 3 indicated the existence of a seven-membered ring, which is composed of ethylenediamine and acetylacetone, inferring a formation mechanism of nucleophilic addition elimination reactions. The synthesis of small molecular rings in complexes 1~3 have not been reported in other systems. In our works, these ring structures precipitated with the host-frames as new products in complexes 1~3, as confirmed by crystal structure analysis and NMR data.