| 氯代(对位取代四苯基)卟啉铁(Ⅲ)的轴向配位反应热力学及光谱研究 |
| THERMODYNAMIC AND SPECTRAL STUDY OF AXIAL COORDINATION OF PARA-SUBSTITUTED TETRAPHENYLPORPHINATOIRON(Ⅲ)CHLORIDE |
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| 摘要: 本文对二氯甲烷溶剂中咪唑(Im)与氯代(对位取代四苯基)卟啉铁(Ⅲ)[Fe(p-X)TPPCl,X=Cl,H,CH3,OCH3]的轴向配位反应(1)进行了研究.用光谱法测得了反应(1)的平衡常数,并对反应物和产Fe(p-X)TPPCl+2Im⇔[Fe(p-X)TPPIm2]+Cl-物的电子光谱、FeHTPPCl和[FeHTPPIm2]+Cl-的电子自旋共振谱和穆斯堡尔谱进行了测量.研究了取代基效应和轴向配体的影响. |
| 关键词: 氯代(对位取代四苯基) 啉铁(Ⅲ) 平衡常数 紫外-可见光谱 电子自旋共振谱 穆斯堡尔谱 |
| 基金项目: 国家科学基金资助的课题 |
Abstract: A thermodynamic study is reported for the axial coordination of para-substituted tetraphenylporphinatoiron(Ⅲ)chloride [Fe(p-X)TPPCl, X=C1, H, CH3, OCH3] with imidazolc(Im)in dichloromethane.  Not only the equilibrium constant(β)of reaction(1)by spectral technique, but also the visible absorption spectra of reactants and products, and ESR spectra and Mossbauer spectra of FeHTPPCl and [FeHTPP(Im)]+Cl- were measured. The standard change of molar enthalpy(ΔHmθ)and standard change of molar entropy(ΔSmθ)of reaction(1)were calculated. The experimental results showed that:l.ΔHmθ and ΔSmθ of reaction(1)are negative values.2. The spin of the iron(Ⅲ)in reactants is s=5/2 and in products is s=1/2. 3. The electron-donating substituents make the bathochromic shift of the charge transfer bands and the increase of the oscillator strength(ƒ)for Fe(p-X)TPPCl.4. The stronger the electron-donating ability,of substituents, the larger the equilibrium constants are. 5. It is found that linear relationships exist between following pairs: ΔHmθ and the Hammett constant δ; lnβ and δ; ν of CT band and δ; ƒ of CT band and δ. |
| Keywords: para-substituted tetraphenylporphinatoiron(Ⅲ)chloride equilibrium constant UV-Vis spectra ESR spectra Mossbauer spectra |
| 投稿时间：1988-06-20 |
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| 朱志昂,马玉新,陈荣悌,张一宝,江冬青.氯代(对位取代四苯基)卟啉铁(Ⅲ)的轴向配位反应热力学及光谱研究[J].无机化学学报,1991,7(2):153-159. |
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