自然界中，細胞色素P450具有將烷類轉化成醇類的重要催化能力，在其反應機制中有許多不穩定的中間體。其中，鐵超氧化物及鐵氫過氧化物擔任極重要的角色。本研究使用實驗室先前所開發之 N3O2 五牙基 H2BDPＲP，將其苯環上𝜌-位置分別置換成溴、甲基與三級丁基。將配位基去質子化後與 FeCl2 反應可生成五配位二價鐵錯合物 Fe(BDPRP)。先與氧氣反應生成鐵超氧化物Fe(BDPRP)(O2•)。此時加入三氟甲磺酸（Trifluoromethanesulfonic acid, HOTf）會反應生成鐵氫過氧化物[Fe(BDPRP)(OOH)](OTf)。利用DBU滴定所確認的pKa值與循環伏安法（cyclic voltammetry, CV）測得的氧化還原半電位可定出三價鐵氫過氧化物 Fe(BDPRP)(OOH)的鍵能及其反應性。另外透過電子順磁共振光譜儀 (Electron Paramagnetic Resonance Spectrometer, EPR)及穆斯堡爾光譜儀 (Mössbauer Spectrometer)初步證明鐵氫過氧化物之鐵中心可能為正四價高自旋S = 2的電子組態。上述研究可幫助我們更詳細地了解由氧合酶之含金屬酵素進行氧氣活化時的反應機制，及所製備之仿生化合物的反應性探討。

In nature, cytochrome P450 possesses a very important catalytic ability of converting alkanes into alcohols. Two active intermediates, iron superoxide and iron hydroperoxide, are essential in the P450 catalytic cycle. In order to produce stable biomimetic intermediates, the N3O2 pentadentate ligand, H2BDPP, developed previously in our laboratory was modified to H2BDPRP (R = Br, Me, tBu). After deprotonation of H2BDPRP by NaH, the resulting ligands was reacted with FeCl2 forming the pentacoordinated Fe(II) complexes Fe(BDPRP).
The Fe(III)-superoxo complexes, Fe(BDPRP)(O2•), were first generated by bubbling O2 into MeTHF solutions of Fe(BDPRP) at – 120 °C. Addition of 1 equiv of trifluoromethanesulfonic acid (HOTf) into the solution of Fe(BDPRP)(O2•) produced the Fe(IV)-hydroperoxo complexes, [Fe(BDPＲP)(OOH)](OTf). If Fe(BDPRP)(O2•) reacted with TEMPOH, the Fe(III)-hydroperoxo complexes, Fe(BDPRP)(OOH), were formed. The bond energies of the OO−H bond in Fe(BDPRP)(OOH) were determined by pKa values confirmed by DBU titration and redox potential (E1/2) obtained by cyclic voltammetry. In addition, Mössbauer and EPR studies on [Fe(BDPtBuP)(OOH)](OTf) preliminary indicate the high-spin (S = 2) FeIV center. The studies described above shed light on understanding more details of the mechanism proceeded in O2 activation carried out by metallo-enzymes of oxygenases and reactivity of our model compounds.

參考資料
1. Kim, H.; Rogler, P. J.; Sharma, S. K.; Schaefer, A. W.; Solomon, E. I.; Karlin, K. D. J. Am. Chem. Soc. 2020, 142, 3104-3116.
2. W. Nam, in comprehensive Coordination Chemistry II, 2003, 8.12, 281-307
3. Roach, P. L.; Clifton, I. J.; H.Hensgens, C. M.; Shibata, N.; Schofield, C. J.; Hajdu, J.; Baldwin, J. E. Nature 1997, 387, 827–830
4. Tamanaha, E.; Zhang, B.; Guo, Y.; Chang, W. C.; Barr, E. W.; Xing, G.; Clair, J. S.; Ye, S. F.; Neese, F.; Bollinger, J. M.; Jr.; Krebs, C. J. Am. Chem. Soc. 2016, 138, 8862−8874
5. Chiang, C. W.; Kleespies, S. T.; Stout, H. D.; Meier, K. K.; Li, P. Y.; Bominaar, E. L.; Que, L.; Jr.; Münck, E.; Lee, W. Z. J .Am. Chem. Soc. 2014, 136, 10846−10849
6. Heather D. Stout ; Scott T. Kleespies ; Chien-Wei Chiang ; Way-Zen Lee ; Lawrence Que, Jr. ; Eckard Münck, and Emile L. Bominaar Inorg. Chem. 2016, 55, 5215−5226
7. 陳昇甫，非血基質三價鐵超氧化及過氧氫化物之合成與反應性，國立臺灣師範大學化學研究所碩士論文，2020
8. Seungwoo, H.; Yong-Min, L.; Woonsup, S.; Shunichi, F.; Wonwoo, N. J .Am. Chem. Soc. 2009, 131, 13910−13911
9. Pritam Mondal ; Izumi Ishigami ; Emilie F. Gérard ; Chaeeun Lim ; Syun-Ru Yeh ; Sam P. de Visser and Gayan B. Wijeratne Chem. Sci., 2021, 12, 8872–8883
10. 游築翔，三氮二氧配位之高自旋非血基質{FeNO}7錯合物的一氧化氮活化反應，國立臺灣師範大學化學研究所碩士論文，2014
11. Nicole Kindermann ; Can-Jerome Günes ; Sebastian Dechert, and Franc Meyer. J. Am. Chem. Soc. 2017, 139, 9831−9834.
12. Hyun Kim ; Patrick J. Rogler ; Savita K. Sharma ; Andrew W. Schaefer ; Edward I. Solomon, and Kenneth D. Karlin. J. Am. Chem. Soc. 2020, 142, 3104−3116.
13. Wilson D. Bailey ; Debanjan Dhar ; Anna C. Cramblitt, and William B. Tolman. J. Am. Chem. Soc. 2019, 141, 5470−5480
14. 林延壕，單核錳金屬超氧錯合物：合成、鑑定及其反應性，國立臺灣師範大學化學研究所碩士論文，2020
15. Yu-Ran Luo, Handbook of Bond Dissociation Energies in Organic Compounds, 2002
16. Michael H. Abraham ; Priscilla L. Grellier ; David V. Prior ; Philip P. Duce ; Jeffrey J. Morris and Peter J. Taylor. J. Chem. Soc. Perk. Trans. 2 1989, 699-711.
17. David A. Quist ; Melanie A. Ehudin ; Andrew W. Schaefer ; Gregory L. Schneider ; Edward I. Solomon ; and Kenneth D. Karlin. J. Am. Chem. Soc. 2019, 141, 12682−12696