臺灣博碩士論文加值系統

雖然說N-confused porphyrin 在最近被許多化學家研究，但是卻還沒在文獻上發現有跟NO相關的文章。我們實驗室成功的將NO2-還原而合成出【MNO】6的Fe(CTPP)NO，或藉由加入NO氣體到錯合物1a 中也能合成出Fe(CTPP)NO(1b)。我們對其相關性質都做了研究，並得到一些研究的結果，測得ν(NO)在1796 cm-1；在晶體中發現Fe(CTPP)NO是一個直線NO的五配位錯合物；測得EPR的g值為2.03 ，因I=1 (14N)所以EPR會有三根訊號，而還原後的Fe(CTPP)NO跟同位素Fe(CTPP) 15NO 的EPR之g值皆為2.03。磁性的結果，在室溫跟低溫下的μeff分別為3.43、0.99。由以上的結果我們判斷Fe(CTPP)NO屬於順磁的【FeIIINO･】6。將Fe(CTPP)NO氧化後可以得到其氧化物，Fe(CTPPO)NO(1c)。這氧化物屬於【MNO】6之NO complex，其IR=1770 cm-1；由晶體結構發現Fe-O-C的鍵結環境中，Fe及C=O 鍵以三環(η2)的鍵結形式存在。
不同的軸配位基對整個化合物的電子組態有相當大的影響。我們試著將起始物的軸配位基置換成其他的配位基，如ClO4－、CF3SO3－、BF4－、NCS－、N3－、NO，目前我們得到Fe(CTPP)NCS晶體結構，其晶體結構顯示Fe與環內C-H間有agostic作用力。

Nitric oxide is a second-messenger which regulates memory, blood coagulation, blood pressure, smooth muscle proliferation, respiration and cell death. Several NO related metalloproteins such as NOase, guanylate cyclase and nitrophorin contain heme as prosthetic group for NO binding. Although N-confused porphyrin chemistry develops rapidly in recent years, their chemistry especially toward the biomimetic chemistry has not been established. In particular, there is no report related to the NO chemistry on recently discovered N-confused porphyrin (CTPP) complexes. The results from our group suggest that the N-confused porphyrin iron complex exhibits nitrite reduction activity to reduce NO2- and form a [MNO]6 Fe(CTPP)NO with a linear NO as a ligand. Fe(CTPP)NO is confirmed to be [FeIIINO･]6 with ν(NO) at 1796 cm-1。 The SQUID result is in agreement with a FeIII center and NO･ state with antiferromagnetic coupling between Iron and NO. The unusual stability of NO on Iron(III) center was attributed to the high charge CTPP3- center which stabilize NO through back-bonding. The discussion on the mechanism suggests that protons provided from the ligand would be the reason for nitrite reduction reaction under mild conditions. From the studies, a novel Fe(CTPPO)NO was also isolated and its crystal structure gives a bent Fe-N-O and η2 interaction between iron and inner C=O. To fine-tune the electron geometry in the iron center, we also carried out axial ligand exchange reaction to replace axial bromide of Fe(HCTPPH)Br with ClO4－、CF3SO3－、BF4－、NCS－、N3－. The crystal structure of Fe(HCTPPH)NCS exhibits a solid state structure similar to its starting compound, Fe(HCTPPH)Br. The iron and inverted internal C-H is within the distance of agnostic interaction.

第一章 一氧化氮異位卟啉鐵錯合物 1

一、緒論 1
（一）異位卟啉化合物 1
（二）異位卟啉配位化學與紫質蛋白關聯 8
（三）一氧化氮與金屬紫質蛋白 11
二、實驗 15
（一）一般實驗製備 15
（二）物理性質的測量 16
（三）化合物的合成與鑑定 17
三、實驗結果與討論 19
四、結論 43
參考文獻 46

第二章 五配位異位卟啉鐵錯合物-軸配位基置換之 49
合成相關研究

一、緒論 49
二、實驗 49
三、實驗結果與討論 51
四、結論 61
參考文獻 63

第三章 未來展望 64
參考文獻 66

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