臺灣博碩士論文加值系統

我們透過[Fe(OMTPP‧)Cl]+、[Fe(OETPP‧)Cl]+兩種不同馬鞍型變形程度的三價鐵卟啉陽離子自由基的晶體結構、1H NMR光譜、磁滯率量測及DFT理論計算，皆顯示兩者具有相似的強dx2-y2－a2u軌域作用。兩種馬鞍型三價鐵卟啉陽離子自由基的變形程度皆較氧化前大，也有類似的1H NMR光譜，他們的光譜數據也符合溶液中結構為高度馬鞍型變形。因此平面卟啉Fe(TPP)Cl經單電子氧化後，可得到類似[Fe(OMTPP‧)Cl]+、[Fe(OETPP‧)Cl]+的光譜結果，顯示其馬鞍型變形程度可能增加導致dx2-y2－a2u軌域作用增強。本文中以DFT理論計算將三種馬鞍型變形卟啉模型透過苯基旋轉及馬鞍型變形調整，發現其相似的NMR光譜具有多種成因。
在另一主題中,我們以TBHP氧化Fe(OETPP)ClO4，在低溫UV-vis量測(OETPP)FeIIIO(H)OtBu的O－O鍵均相斷鍵動力學參數(ΔHǂ = 47(2) kJ mol-1，ΔSǂ = 83(9)J mol-1K-1)，並透過低溫1H NMR及ESI-MS鑑定得到與四價鐵等電子數的 [Fe(OETPP‧)OH]+，且發現斷鍵後的·OtBu自由基會再對三價鐵進行氧化形成 [Fe(OETPP‧)OtBu]+。除此之外，三價鐵卟啉陽離子自由基仍會與過量的TBHP反應，得到與四價鐵卟啉陽離子自由基(通稱為Compound I)等電子數的三價鐵異卟啉。最後，我們利用三價鐵異卟啉於二氯甲烷中催化環己烯，得到以溶劑作為氯的來源且具有高選擇性的結果。

In this study, paramagnetic NMR spectroscopy, X-ray diffraction, magnetic susceptibility and DFT calculation are employed to elucidate the strong bonding interaction between iron(III) dx2-y2 and porphyrin a2u orbitals of [Fe(OMTPP∙)Cl]SbCl6 and [Fe(OETPP∙)Cl]SbCl6. Their crystal structures clearly indicate that their saddle deformations are increased compared to those prior to oxidations. Their 1H NMR data present the S = 2 states for such one-electron oxidation states, and demonstrate that their structures in solutions remain strong saddle deformations. In light of 1H NMR spectroscopy of [Fe(TPP∙)Cl]SbCl6 resembling to the above cases, we postulate that the ring structure of [Fe(TPP∙)Cl]+ may possess strongly saddle to have great bonding interaction between iron(III) dx2-y2 and porphyrin a2u orbitals. In the DFT calculations, the degrees of phenyl ring rotation and saddled deformation will also affect their NMR spectra.
In another topic, we observe O-O bond homolytic cleavage of (OETPP)FeIIIO(H)OtBu formed in the reaction of Fe(OETPP)ClO4 with TBHP and its activation parameters (ΔH≠ = 47(2) kJ mol-1, ΔS≠　= 83(9)J mol-1K-1) is measured by low-temperature UV-vis spectral data. The corresponding one-electron oxidation product is identified as [Fe(OETPP∙)OH]+, which is an isoelectronic structure as oxoiron(IV) porphyrin, by UV-vis, NMR spectroscopy and ESI-MS spectrometry. According to the experiments of NMR and ESI-MS, we also find that ·OtBu radical will convert Fe(OETPP)ClO4 to [Fe(OETPP∙)OtBu]+. Furthermore, these related iron(III) porphyrin radical cations can be carried out one more electron oxidation to isoporphyrins, an isoelectronic structure as Compound I. These iron(III) saddled isoporphyrins are shown to be reactive for highly selective chlorination of cyclohexene.

第一章、卟啉模型化合物的研究介紹 1
一、血紅素系統 1
(一)提供軸向配基 2
(二)形成疏水袋 2
(三)形成氫鍵 2
(四)造成大環變形 2
(一)可逆的氧合作用 2
(二)氧的還原活化 3
二、金屬卟啉模型化合物 5
三、非平面卟啉 7
四、金屬卟啉的電子組態 11
五、順磁核磁共振光譜 14
(一)吸收峰變寬 14
(二)化學位移範圍變大 16
(三)受鍵結影響 17
(四)受溫度影響 24
第二章、八烷基四苯基鐵卟啉之合成 25
一、前言 25
二、儀器設備 26
三、藥品 27
四、三價鐵卟啉的合成 29
(一) Fe(OMTPP)Cl的合成 29
(二) Fe(OETPP)Cl及Fe(OETPP)ClO4的合成 32
第三章、三價鐵卟啉陽離子自由基的光譜研究 36
一、前言 36
二、實驗部分 38
(一) 儀器設備 38
(二) 藥品 38
(三) 單電子氧化劑的合成 39
(四) 1H NMR光譜 40
(五) X-ray晶體結構 42
(六) 磁滯率量測 45
(七) 應用理論計算 45
三、結果與討論 46
四、結論 58
五、附件 59
第四章、Hydroxo Iron(III) Radical Cation光譜研究及O－O鍵均相斷鍵模型 61
一、前言 61
二、實驗部分 65
(一) 儀器設備 65
(二) 藥品 65
(三) d1-TBHP的合成 66
(四) 碘滴定法 67
(五) 以光譜追蹤三價鐵卟啉與過氧化物的反應 67
(六) [Fe(OETPP·)Br]ClO4 的鑑定 69
三、結果與討論 71
(一) Hydroxoiron(III) radical cation 光譜鑑定 71
(二) 動力學 80
(三) 溶劑效應 85
四、結論 92
第五章、異卟啉的研究 94
一、前言 94
二、實驗部分 95
(一) 以光譜追蹤異卟啉生成反應 95
(二) 催化反應 96
三、結果與討論 98
(一) 異卟啉光譜偵測 98
(二) 催化反應之結果 109
四、結論 111
第六章、總結論 112
參考文獻 113
附件 118
附錄一、[Fe(OETPP·)Br]ClO4　-80 °C至30 °C之變溫NMR光譜 118
附錄二、Fe(OETPP)ClO4的晶體數據 120
附錄三、[Fe(OMTPP·)Cl]SbCl6的晶體數據 124
附錄四、[Fe(OETPP·)Cl]SbCl6的晶體數據 128
附錄五、[Fe(OETPP·)Br]ClO4的晶體數據 132

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