一些大取代二茂铁三碘化物的合成和结构分析  

Synthesis and Structure Analysis of Some Bulkily Substituted Ferrocenium Triiodides

作　　者：李金山[1] 熊传辉 张经坤[2] 刘成[2] 白京生 

机构地区：[1]南开大学元素有机化学研究所,天津300071 [2]南开大学中心实验室,天津300071

出　　处：《化学学报》1999年第4期423-430,共8页Acta Chimica Sinica

摘　　要：合成了一系列大取代二茂铁三碘化物,通式为(RC_5H_4)_2FeI_3.通过元素分析,红外光谱,质谱,顺磁共振谱,穆斯堡尔谱和电导率对这些化合物进行了表征.测定了化合物[CH_2(CH_2)_3C(2-CH_2C_5H_4N)C_5H_4]_2FeI_4·H_2O的晶体结构,该晶体属三斜晶系,P-1空间群,晶胞参数:a=0.9593(1),b=1.3999(2),c=1.4537(2)nm.α=109.64(1),β=97.25(1),γ=104.69(1)°.V=1.7299nm^3,M_r=1030.13,D_x=1.98g/cm^3,Z=2.结果表明,取代二茂铁被碘部分氧化,导致中心金属铁表现为混合价态;由于茂环上大取代基的影响,使得I_3^-与I_3^-之间未能形成碘链,因此这些化合物的电导率很低。A series of bulkily substituted ferrocenium triiodides with general formula (RC5H4)2FeI3 have been synthesized and characterized by elementary analysis, IR spectrum, mass spectrum, ESR spectrum, Mossbauer spectrum and conductivity. The crystal structure of [CH2(CH)2)3C (2 - CH2C5H4N) C5H4]2FeI4·H2O has been determined. The crystal belongs to triclinic, space group P - 1, The cell parameters are a =0.9593(1), 6 = 1.3999(2), c = 1.4537(2)nm. α = 109.64(1), β = 97.25(1), γ= 104.69(1)°. V=1.7299nm3, Mr=1030.13, Dx = 1.98g/cm3, Z = 2. The results indicate that the substituted ferrocene is partially oxidized by iodine, therefore the central metal iron shows mixed valence state. Because of the effect of bulky substituents in cyclopentadienyl ring the polyiodide chains of the I3- ions are not formed, the conductivities of these compounds are very low.

关 键 词：二茂铁正离子 混合价态 晶体结构 三碘化物 取代 

分 类 号：O627.81[理学—有机化学]