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研究生： 王俊傑
Wang, Chun-Chieh
論文名稱： 三價鈷超氧化物之合成與反應性之研究
Formation of Cobalt(III)–Superoxo Complex and Its Reactivity
指導教授： 廖文峯
Liaw, Wen-Feng
口試委員: 鄭建鴻
Cheng, Chien-Hung
江昀緯
Chiang, Yun-Wei
洪政雄
Hung, Chen-Hsiung
李位仁
Lee, Way-Zen
學位類別： 博士
Doctor
系所名稱： 理學院 - 化學系
Department of Chemistry
論文出版年： 2018
畢業學年度： 107
語文別： 英文
論文頁數： 144
中文關鍵詞： 超氧錯合物 、過氧氫化合物 、過氧亞硝酸鹽 、過氧亞硝基錯合物
外文關鍵詞： Superoxo, Hydroperoxo, Peroxynitrito, Peroxynitrite
相關次數： 點閱：2  下載：0 
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    • 本實驗中，在−90 ℃的狀態下，將氧氣通入至錯合物CoII(BDPP) (1)的THF溶液中，進而生成三價鈷的超氧錯合物中間體CoIII(BDPP)(O2) (3)。並經由在EPR光譜上觀察到超精細交互作用的現象與ESEEM光譜上觀測到自旋電子與氮的相互作用，得知錯合物3的中心金屬CoIII與超氧化物配位基上的單電子形成了較弱的交互作用。值得一提的是，將三價鈷之超氧化物中間體與TEMPOH反應，並進行氫原子轉移過程後，可得到三價鈷之過氧氫化合物CoIII (BDPP)(OOH) (4)及其晶體。除此之外，在本研究中還提出了錯合物4的其他合成途徑，其可以經由[CoIII(BDPP)(H2O)]( BF4) (2)與過量的H2O2和NEt3反應，亦或者將錯合物1直接與過量的H2O2反應來製備。理論計算中得到的錯合物3和4的DFT優化結構，可以與共振拉曼光譜中的特徵震動吸收值相互驗證。錯合物 4之晶體與優化結構都說明了第六配位基上的過氧氫化合物的質子與配位基BDPP2−上的氧原子形成了分子內氫鍵。這種逐步分析氧氣活化的過程研究，將有助於了解鈷金屬與氧氣反應來進行的相關催化反應。
    另一方面，本研究提出了首次長壽命型的非血基三價鈷金屬的過氧亞硝基錯合物CoIII(BDPRP)(OONO) (R = H (7)，Br (8))，其本身可經由三價鈷的超氧化物中間體，在−90 ℃的狀態下與NO(g)反應而得。使用15N NMR和低溫反應IR測量可以提供錯合物8的存在證據，而不是使用常見的酚類化合物之硝化反應來證明。更重要的是，錯合物[CoIII(BDPRP)(H2O)]( NO3−) (R = H (9)，Br(10))可經由將錯合物7和錯合物8的溶液，使之升溫至環境溫度來形成，錯合物9和10的晶體結構均顯示CoIII中心除了與水分子和BDPRP2−配位，還與硝酸根離子形成陰陽離子配位，其中的硝酸根陰離子被認為源自於過氧亞硝酸鹽（PN）的分子間異構化所形成的。除此之外，實驗中發現CoIII(BDPRP)(NO) (11)其自身經由一氧化氮的初始解離與隨後氧氣的快速重新結合，提供此特殊的反應途徑，且與亞鐵HbNO的自動氧化的第一步反應具有一致性。最後，本研究藉由穩定的三價鈷金屬之過氧亞硝基錯合物提供了的錯合物9和10的完整形成的機制，期望可以對於生化上此相關的研究，提供更新更完整的見解。

    Bubbling O2 into a THF solution of CoII(BDPP) (1) at −90 °C generates a cobalt-superoxo intermediate, CoIII(BDPP)(O2) (3). The CoIII center of complex 3 is weakly coupled with the O2•− ligand showing superhyperfine coupling measured in EPR and spin–nitrogen interaction observed by ESEEM. Significantly, the structurally characterized cobalt(III)–hydroperoxo complex, Co(BDPP)(OOH) (4), was produced from the superoxo intermediate via hydrogen atom abstraction from 2,2,6,6-tetramethyl-1-hydroxypiperidine (TEMPOH). In addition, other synthetic pathways of complex 4 are presented in our work, which can be prepared by either reacting [CoIII(BDPP)(H2O)](BF4) (2) with excess H2O2 and NEt3 or the reaction of complex 1 with excess H2O2 without NEt3. DFT-optimized structures of complex 3 and 4 are verified by resonance Raman frequencies of O–O stretching. Both X-ray and optimized structures of complex 4 suggest intramolecular hydrogen bonding between hydroperoxo proton and one of BDPP2− oxygens. Such stepwise dioxygen activation helps to rationalize cobalt-catalyzed aerobic oxidations.
    Furthermore, we present the first longevity of nonheme cobalt(III)–peroxynitrito complex CoIII(BDPRP)(OONO) (R = H (7), Br (8)) derived from its superoxo intermediate with NO(g) at −90 °C. Using a 15N NMR measurement and low-temperature react IR could provide prominent evidence of complex 8, instead of nitration of phenolic compounds in our system. Notably, [CoIII(BDPRP)(H2O)](NO3−) (R = H (9), Br (10)) can be formed by warming up the solution of complex 7 and complex 8 to ambient temperature; The crystal structures of complexes 9 and 10 both reveal that the CoIII center is coordinated by an aqua moiety, BDPRP2− and a nitrate anion which is presumed to be derived from intermolecular isomerization of peroxynitrite (PN) ligand. The cobalt(III)–nitrosyl complex (11), moreover, provides a particular reaction route via an initial dissociation of NO(g) and rapid rebinding of O2 subsequently which is in accord with the first step of autoxidation of ferrous HbNO. Hence, we afford a compelling formation mechanism of complexes 9 and 10 through the intermediate, cobalt–peroxynitrito species in this study.

    CHAPTER ONE INTRODUCTION 1 Non-Heme Iron-Containing Enzyme 1 Isopenicillin N Synthase (IPNS) 2 myo-Inositol Oxygenase (MIOX) 3 Homoprotocatechuate 2,3-Dioxygenase (2,3-HPCD) 5 Hydroxyethylphosphonate Dioxygenase (HEPD) 6 Model Complexes of Non-Heme Fe–Superoxo Enzyme 8 Cobal-Superoxot Model Complexes 10 Bleomycins 13 Iron Bleomycin 17 Cobalt-Substituted Bleomycin 18 Model Complexes of Fe–Bleomycin 21 Peroxynitrite 23 Peroxynitrite Generated from Model Complexes 28 CHAPTER TWO EXPERIMENTAL SECTION 33 General Procedures and Materials. 33 Generation of Isotope-Labeled 15NO(g) 34 Instrumentation 35 Nuclear Magnetic Resonance 35 Absorption Spectroscopy 35 Cyclic Voltammetry 35 Elemental Analyses 36 Magnetic Measurements 36 Crystallography 36 CW/Pulsed EPR Measurements 37 Resonance Raman Measurements 38 IR measurement 38 IR measurement at low temperature 38 GC-Mass Measurements 38 ESI-Mass Measurements 39 Experiment 39 Synthesis of H2BDPRP 39 Preparation of TEMPOH 40 Synthesis of Co(BDPP) (1) 40 Synthesis of [Co(BDPP)(H2O)](BF4) (2) 41 Preparation of Co(BDPP)(O2) (3) 41 Synthesis of Co(BDPP)(OOH) (4) 41 Synthesis of Co(BDPBrP) (5) 42 Preparation of Co(BDPBrP)(O2) (6) 42 Synthesis of Co(BDPP)(OONO) (7) 42 Synthesis of Co(BDPBrP)(OONO) (8) 43 Synthesis of [Co(BDPP)(H2O)](NO3) (9) 43 Synthesis of [Co(BDPBrP)(H2O)](NO3) (10) 43 Synthesis of Co(BDPBrP)(NO) (11) 44 Synthesis of Co(BDPBrP)(NO2) (12) 44 Formation of TEMPO Radical from the Reactivity of Complex 3 with TEMPOH 44 Kinetic Study of Co(BDPP)(O2) towards TEMPOH 45 Preparation of Complex 4 from the Reaction of 2 with Excess H2O2 and NEt3 47 Preparation of Complex 4 from the Reaction of 1 with Excess H2O2 47 Measurement of 15N NMR Samples 47 ESI-MS Analysis of [Co(BDPBrP)(H2O)](NO3) Labeled with 15NO(g) or 18O2(g) 48 GC-MS Analysis of Phenol Products Derived from the Reaction between Cobalt(III)-Peroxynitrito Intermediate and 2,4-DTBP 49 Computational Details 51 CHAPTER THREE RESULTS AND DISCUSSION 66 General Characterization of Co(BDPP) (1) and [Co(BDPP)(H2O)](BF4) (2) 66 Formation of Cobalt(III)-Superoxo, Co(BDPP)(O2) (3), and Its Characterization 72 General Characterization of Co(BDPBrP) (5) 78 Formation of Cobalt(III)-Superoxo, Co(BDPBrP)(O2) (6), and Its Characterization 80 Reactivity of Superoxo 82 Formation of Co(BDPP)(OOH) (4) and Its Characterization 82 DFT Calculations for Complex 1, 3, 4 and 4′ 91 Characterization and Reaction of Co(BDPRP)(O2) (R = H (3), Br (6)) and Nitric Oxide 94 Formation of [Co(BDPRP)(H2O)](NO3) (R = H (9), Br (10)) and Its Characterization 98 Reaction of Co(BDPBrP), NO and O2 Yielding Cobalt-Superoxo 108 CHAPTER FOUR CONCLUSION AND FUTURE WORK 110 I. Formation of Co(BDPP)(OOH) (4) and Its Characterization 110 II. Reaction of Co(BDPRP)(O2) (R = H (3), Br (6)) with Nitric Oxide Generating the Cobalt-Peroxynitrito Complexes, Co(BDPRP)(OONO) (R = H (7), Br (8)) 111 Proposed Future Work: Active Species such as Carbonate Radical and Nitrogen Dioxide Generated via a Reaction of Peroxynitrite with CO2 112 Reference 114 APPENDIX I

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