在許多的含錳酵素催化循環中，高價態錳氧錯合物與錳的過氧烷錯合物被認為是可能存在的反應中間物，特別是第二光系統(Photosystem II)中的氧釋放複合體(Oxygen-Evolving Complex)、含錳雙加氧酶(Manganese-Dependent Dioxygenase)和含錳脂氧合酶(Mn-Lipoxygenase)，為了能模擬這些在酵素反應中的中間物，本研究利用實驗室所開發的三價錳錯合物：[MnIIIBDPP(H2O)]PF6 (2)、MnIIIBDPP(OH) (5)。錯合物(2)可以透過氧化劑Magic Blue (Tris(4-bromophenyl) aminium hexachlorido antimonate)氧化成錯合物(6)，再加入有機鹼DBU會反應成錯合物(7)，推測錯合物(6)與(7)分別為[MnIVBDPP(H2O)]2+和[MnIVBDPP(OH)]+，也透過UV-vis光譜和EPR光譜來鑑定為高自旋四價錳錯合物(S = 3/2)，還利用苯酚衍生物證實錯合物(7)能作氫原子轉移。錯合物(5)加入cumene hydroperoxide後形成錯合物(8)，還可以透過Magic Blue氧化形成錯合物(9)，推測錯合物(8)、(9)為MnIIIBDPP(OOCm)和[MnIVBDPP(OOCm)]+，以UV-vis光譜和EPR光譜來鑑定為高自旋四價錳錯合物(S = 3/2)，同時利用2-PPA作O-O鍵裂解，也利用1,4-CHD作C-H鍵活化。

High valent manganese oxygen species and manganese alkylperoxo are proposed intermediates in the catalytic cycles of most manganese containing enzymes, especially for Oxygen-Evolving Complex in Photosystem II, Manganese-Dependent Dioxygenase, and Mn-Lipoxygenase. In order to simulate these intermediates, this study utilizes a serial of MnIIIBDPP complexes developed by our laboratory : [MnIIIBDPP(H2O)]PF6 (2), MnIIIBDPP(OH) (5), were prepared. (2) can be oxidized to (6) by an oxidant as Magic Blue (Tris(4-bromophenyl) aminium hexachlorido antimonate), and then the organic base DBU is added to react into (7). (6) and (7) are speculated [MnIVBDPP(H2O)]2+ and [MnIVBDPP(OH)]+ when we identified as high-spin quaternary manganese complex by UV-vis spectroscopy and EPR spectroscopy (S = 3/ 2). We also used phenol derivatives to confirm that (7) can do HAT. We added cumene hydroperoxide (5) to form (8), and added Magic Blue to oxidize (8) to (9). We assumed that (8) and (9) are MnIIIBDPP(OOCm)and [MnIVBDPP(OOCm)]+ respectively. UV-vis spectroscopy and EPR spectroscopy were used to identify high-spin quaternary manganese complexes (S = 3/2), while 2-PPA was used for O-O bond cleavage, and 1,4-CHD was also used for C-H bond activation.

1. 2013, 朱其翊學長碩士論文
2. Kamiya, N.; Kawakami, K.; Umena, Y. Nature 2011, 473, 55–60.
3. Noguchi, T. J. Am. Chem. Soc. 2017, 139, 2022−2029
4. Cox, N.; Lubitz, W. Science. 2014, 345, 804–808
5. Allakhverdiev, S. I.; Najafpour, M. M. Chem. Rev. 2016, 116, 2888–2936
6. Pollock, C. J.; Silakov, A.; Krebs ,C; Bollinger, J. M., Jr J. Am. Chem. Soc. 2017, 139, 1950–1957
7. Oliw, E. H.; Karkehabadi, S. J. Biol. Chem., 2016, 291, 8130–8139
8. Valentine, J. S.; Teixeira, M.; Miller, A. F.; Maroney, M. J.; Cabelli, D. E.;Abreu, I. A. Chem. Rev. 2014, 114, 3854–3918
9. Fujii, H. Inorg. Chem. 2010, 49, 6664–6672
10. Fujii, H. Inorg. Chem. 2008, 47, 1674–1686
11. Borovik, A. S.;Hendrich, M. P.; Yano, J. Chem. Sci., 2014, 5, 3064–3071
12. Borovik, A. S.; Hendrich, M. P. Inorg. Chem. 2013, 52, 12568–12575
13. Busch, D. H. J. Am. Chem. Soc. 2008, 130, 16245–16253
14. Jackson, T. A. Inorg. Chem. 2016, 55, 3272–3282
15. Stack, T. D. P. J. Am. Chem. Soc. 2005, 127, 9904–9912
16. Borovik, A. S. J. Am. Chem. Soc. 2003, 125, 13234–13242
17. Kovas, J. A. Inorg. Chem. 2013, 52, 12383–12393
18. Jackson, T. A. Inorg. Chem. 2014, 53, 7622–7634
19. Jackson, T. A. Inorg. Chem. 2016, 55, 8110−8120
20. McDonald, A. R. J. Am. Chem. Soc. 2016, 138, 14362–14370
21. Goldberg, D. P. J. Am. Chem. Soc. 2012, 134, 16619–16634
22. Que, L., Jr.; Farquhar, E. R.; Emerson, J. P. PNAS., 2008, 105, 7347–7352
23. Lee, W.-Z.; Münck, E.; Que, L., Jr.; Bominaar, E. L. J. Am. Chem. Soc., 2014, 136, 10846–10849
24. Lee, W.-Z.; Liaw, W.-F.; Tasi, M.-L.; Ye, S.-F. J. Am. Chem. Soc., 2016, 138, 14186–14189
25. Fukuzumi, S.; Nam, W. J. Am. Chem. Soc. 2018, 140, 12695−12699
26. Goldberg, D. P. J. Am. Chem. Soc. 2018, 140, 4380−4390
27. Anderson, J. S. J. Am. Chem. Soc. 2018, 140, 13176−13180
28. Richards, N. G. J. Essays. Biochem. 2017, 61, 259-270
29. Bornemann. S. Biochem. J. 2007, 407, 397-406
30. Brudvig. G. W. Photochem. Photobiol. Sci. , 2005, 4 , 940–949
31. Neese. F.; Ye, S.-F. Chem. Sci., 2012, 3, 1600–1611
32. Mascharak. P. K. J. Am. Chem. Soc. 1998, 120, 9015-9027
33. Itoh. S. J. Am. Chem. Soc. 2008, 130, 4244-4245
34. Kovacs. J. A. J. Am. Chem. Soc. 2013, 135, 4260-4272
35. Cho. J. Chem. Commun., 2017, 53, 9328--9331