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Please use this identifier to cite or link to this item: http://hdl.handle.net/11455/16748
標題: 大環變形對三價鐵卟啉電子組態的影響
Ring Deformation Mediated Electronic Structure of Iron(III) Porphyrins
作者: 劉之誠
Liu, Chih-Cheng
關鍵字: Iron Porphyrins;鐵卟啉
出版社: 化學系所
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摘要: 
金屬卟啉π陽離子自由基在生物的酵素催化反應中扮演關鍵性的角色，如細胞色素P450、過氧化氫酶以及過氧化物酶等系統中的Compound I，其中金屬未偶電子與卟啉自由基未偶電子之間的交互作用，也就是所謂的自旋偶合(spin coupling)，可能調控這個中間物在不同系統中呈現不同的催化活性。
1986年Reed等人針對高自旋三價鐵卟啉π陽離子自由基的自旋偶合首先提出較明確的說法，他認為環變形是造成反鐵磁偶合電子組態形成的原因。本文中利用理論計算所得核電子自旋密度與文獻報導核磁共振光譜中等向位移部分比對與Reed論述符合，六配位錯化物為高自旋三價鐵與卟啉a2u鐵磁偶合，五配位為高自旋三價鐵與卟啉環a2u反鐵磁偶合；透過鍵結分析得知結構對稱降低至C2v可增加a2u-dx2-y2的鍵結作用，使系統更穩定。尤其重要的是，為了穩定a2u π陽離子自由基，環氧化伴隨著大環與meso位置苯環雙邊角變小，五配位錯化物因此產生馬鞍型變形，六配位錯化物則呈現些微波浪型變形，然而波浪型變形不影響其鐵磁偶合的特性。
為了探討大環變形對自旋偶合的影響，我們選擇馬鞍型變形卟啉OETPP系統，成功的利用Cl2、Br2、I2、以及照光反應，得到一系列五、六配位鐵卟啉陽離子自由基，並測得NMR光譜。由五配位錯合物[FeIII(OETPP+˙)Br]+、[FeIII(OETPP+˙)Cl]+晶體得知大環與苯環雙邊角也有變小的趨勢，馬鞍型變形增加，並有明顯的皺摺型變形，且卟啉內環16原子間鍵長有長短交替現象，對稱由C2v下降至C2，為典型a1u與a2u混合之環氧化的特徵。我們試著用理論計算分析其電子組態，結果與[FeIII(TPP+.)Cl]+錯化物同為高自旋三價鐵與卟啉環a2u非定域化反鐵磁偶合。利用鍵結分析去探討卟啉環進一步變形導致對稱低至C2之可能原因，發現OETPP環氧化導致a1u、a2u軌域能量接近，藉由Jahn-Teller distortion，降低對稱，a1u與a2u的混合可使陽離子自由基更加穩定。
已知大環變形有助於中自旋電子組態的形成，中自旋電子組態有兩種不同的型式(dxy2dxz1dyz1dz21- dxy和dxz,yz3dxy1dz21- dπ)。本文針對兩個具有明顯中自旋貢獻的五配位錯化物Fe(OETPP)X (X = NCS, C(CN)3)探討其電子組態的差異。結合NMR 光譜數據與理論計算的分析，由於軸配基NCS-與C(CN)3-鍵結性質的差異，Fe(OETPP)(NCS)之中自旋電子組態以dxy為主，而Fe(OETPP)(C(CN)3)則以dπ為主。而這也是在五配位錯化物系統中，第一次可利用軸配基調控出不同中自旋電子組態的首例。
最後，延續實驗室方雅貞學姐對六配位[Fe(OETPP)(tBuNC)2]+電子組態的研究，顯示可能存在二價鐵卟啉π陽離子自由基的貢獻。在本文中，一方面延續先前研究，發現低自旋二價鐵卟啉a2u π陽離子自由基電子組態，卟啉環上原子所得的電子密度與順磁NMR比對十分符合，但軸上正的電子密度太大，與NMR得到負的化學位移完全不符，經鍵結分析得知卟啉a2u軌域和軸上軌域有鍵結作用，電子密度來自a2u軌域未偶電子。因此在卟啉環中加入皺摺型變形，降低對稱使a2u與軸上鍵結變弱，經理論計算結果大大降低了軸上電子密度。此外，軸配基與大環的夾角變小也有助於降低軸上電子密度。此外我們也成功合成出馬鞍型變形更大的新卟啉OiPTPP，檢視獲得的晶體，卟啉環馬鞍型變形程度比OETPP大很多，配合強場軸配基有機會得到純的二價鐵卟啉π陽離子自由基之電子組態。
URI: http://hdl.handle.net/11455/16748
其他識別: U0005-2108200916410500
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