CAJ | 학술논문

以二茂铁炔烃为原料通过“一锅法”环加成反应合成了一系列2,5-双二茂铁基-1-苯基-吡咯衍生物,包括：2,5-双二茂铁基-1-(3-三氟甲基苯基)-吡咯(1),2,5-双二茂铁基-1-(4-氟苯基)-吡咯(2),2,5-双二茂铁基-1-苯基-吡咯(3),2,5-双二茂铁基-1-(4-乙基苯基)-吡咯(4)和2,5-双二茂铁基-1-(4-乙氧基苯基)-吡咯(5),使用元素分析,傅里叶变换红外(FTIR)光谱,质谱(MS)和核磁共振(NMR)等手段对化合物进行了结构表征。采用循环伏安法(CV),密度泛函理论(DFT)模拟计算研究了苯基上取代基对双二茂铁间电荷交互的影响。研究发现第一氧化电位(Ea1),峰电位差(ΔE)与取代基的哈米特常数(σ),吡咯1H NMR的化学位移(δ),吡咯N原子自然轨道(NBO)电荷之间存在显著线性关联；同时发现,N原子电荷密度升高,双二茂铁间电荷交互能力减弱,N原子电荷密度降低,双二茂铁间电荷交互能力提高。因此这类双二茂铁基吡咯衍生物中N原子电荷密度对双二茂铁间电荷交互起着关键的影响作用。
이이무철결경위원료통과“일과법”배가성반응합성료일계렬2,5-쌍이무철기-1-분기-필각연생물,포괄：2,5-쌍이무철기-1-(3-삼불갑기분기)-필각(1),2,5-쌍이무철기-1-(4-불분기)-필각(2),2,5-쌍이무철기-1-분기-필각(3),2,5-쌍이무철기-1-(4-을기분기)-필각(4)화2,5-쌍이무철기-1-(4-을양기분기)-필각(5),사용원소분석,부리협변환홍외(FTIR)광보,질보(MS)화핵자공진(NMR)등수단대화합물진행료결구표정。채용순배복안법(CV),밀도범함이론(DFT)모의계산연구료분기상취대기대쌍이무철간전하교호적영향。연구발현제일양화전위(Ea1),봉전위차(ΔE)여취대기적합미특상수(σ),필각1H NMR적화학위이(δ),필각N원자자연궤도(NBO)전하지간존재현저선성관련；동시발현,N원자전하밀도승고,쌍이무철간전하교호능력감약,N원자전하밀도강저,쌍이무철간전하교호능력제고。인차저류쌍이무철기필각연생물중N원자전하밀도대쌍이무철간전하교호기착관건적영향작용。
2,5-Diferrocenyl-1-(3-trifluorom-ethylphenyl)-pyrrole (1), 2,5-diferrocenyl-1-(4-fluorophenyl)-pyrrole (2), 2,5-diferrocenyl-1-phenyl pyrrole (3), 2,5-diferro-cenyl-1-(4-ethylphenyl)-pyrrole (4), and 2,5-diferrocenyl-1-(4-ethoxyphenyl)-pyrrole (5) were prepared by the one-pot cycloaddition reaction of ferrocenyl alkyne. The 2,5-diferrocenyl-1-phenyl-1-pyrrole derivatives were characterized by elemental analysis, Fourier-transform infrared (FTIR) spectroscopy, mass spectrometry (MS), and nuclear magnetic resonance (NMR) spectroscopy. The influence of substituents at the phenyl moiety on the electronic interaction was studied using cyclic voltammetry (CV) and density functional theory (DFT) calculations. A linear relationship was observed between the first oxidation potential (Ea1), oxidation potential difference (ΔE) with Hammett constant (Hammettσ) of the substituent, pyrrole 1H NMR chemical shift (δ), and pyrrole N natural bond orbital (NBO) charge. A high N charge density weakened the electronic interaction, and vice versa. Electron transfer between the two ferrocenyl units of these diferrocenyl pyrrole derivatives was influenced by the N charge density.