Please use this identifier to cite or link to this item: http://hdl.handle.net/11455/16628
標題: 以對稱調控高自旋三價鐵卟啉自由基之自旋偶合
Symmetry-controlled Spin Coupling in High spin Iron(Ш) Porphyrin Radicals
作者: 吳欣儒
Wu, Hsin-Ru
關鍵字: Spin coupling;自旋偶合
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。其中六配位錯合物FeIII(TPP+.)(OClO3)2大環為平面結構,高自旋三價鐵五個未偶電子所屬軌域與卟啉a2u自由基對稱不同,呈現鐵磁偶合(ferromagnetic coupling);而五配位錯合物[FeIII(TPP+.)Cl]+則呈現反鐵磁偶合(antiferromagnetic coupling),應與其馬鞍型變形對稱降低,磁軌域(magnetic orbitals)間可產生鍵結作用有關。為了深入了解對稱對金屬卟啉π陽離子自由基自旋偶合的影響,本論文中結合1H、13C NMR、DFT理論計算、以及晶體結構等,詳細探討五、六配位高自旋三價鐵卟啉π陽離子自由基在不同變形系統中的電子特性。
針對TPP系統,計算所得核電子自旋密度與文獻報導順磁等向位移比對結果與Reed的論述僅部份相符,六配位為高自旋三價鐵a2u卟啉反鐵磁偶合,五配位錯合物較符合中自旋三價鐵a1u卟啉鐵磁偶合。根據對稱分析,C4v五配位錯合物透過dz2-a2u的鍵結作用即足以產生反鐵磁偶合。馬鞍型變形降低對稱(C4v → C2v),一方面提高dz2-a2u的作用程度,同時增加dx2-y2-a2u之間的鍵結機會,這些鍵結作用使得dx2-y2軌域能量上升,a2u軌域能量下降,因而產生中自旋三價鐵a1u卟啉陽離子自由基。
對於馬鞍型變形的卟啉OETPP而言,除了可以有機自由基氧化之外,我們成功的利用Cl2、Br2、I2等氧化劑,分別獲得兩種不同配位形式,相當穩定的氧化產物,並測得清晰的1H、13C NMR光譜。五配位錯合物[Fe(OETPP+.)Br]+ 的晶體結構具有馬鞍型加上皺摺型變形,且其中十六圓環呈現鍵長長短交替,典型環氧化的特徵。出乎意料之外的是,計算各種可能電子組態所得核電子自旋密度與NMR光譜順磁等向位移比對結果顯示其為四價鐵卟啉而非三價鐵卟啉π陽離子自由基。
至於另一種具有較高對稱性的氧化產物,根據相關1H、13C NMR以及晶體數據顯示可能是六配位錯合物Fe(OETPP+.)(X)2 ( X = ClO4-、Cl-、Br-、I- ),現階段DFT理論計算顯示其電子組態較符合中自旋三價鐵a1u卟啉鐵磁偶合。
URI: http://hdl.handle.net/11455/16628
其他識別: U0005-2507200711491800
Appears in Collections:化學系所

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