Title Page

Contents

List of abbreviations 16

General Abstract 17

General Introduction 18

General References 20

Chapter Ⅰ. Electrophilic Reactivity of a Mononuclear Nonheme Fe(III)-O₂ Intermediate bearing a 13-Membered Macrocyclic Ligand 23

Abstract 24

Ⅰ-1. Introduction 25

Ⅰ-2. Experimental Section 27

Ⅰ-2-1. Materials 27

Ⅰ-2-2. Instrumentation 27

Ⅰ-2-3. Generation of [FeIII(O2)(13-TMC)]⁺ (1) Species[이미지참조] 28

Ⅰ-2-4. Kinetic Measurements and Product Analysis 29

Ⅰ-3. Results and Discussion 30

Ⅰ-3-1. Characterization of [FeIII(O2)(13-TMC)]⁺ (1)[이미지참조] 30

Ⅰ-4. Reactivity of [FeIII(O2)(13-TMC)]⁺ (1)[이미지참조] 37

Ⅰ-4-1. Oxidation of PhCHO Derivatives by [FeIII(O2)(13-TMC)]⁺ (1)[이미지참조] 37

Ⅰ-4-2. Hydrogen Atom Transfer Reactions by [FeIII(O2)(13-TMC)]⁺ (1)[이미지참조] 46

Ⅰ-5. Conclusion 50

Ⅰ-6. References 51

Chapter Ⅱ. Aromatic Hydroxylation by a Mononuclear Nonheme Fe(IV)(O) Intermediate bearing a 13-Membered Macrocyclic Ligand 54

Abstract 55

Ⅱ-1. Introduction 56

Ⅱ-2. Experimental Section 57

Ⅱ-2-1. Materials 57

Ⅱ-2-2. Instrumentation 57

Ⅱ-2-3. Generation of [FeIV(O)(13-TMC)]²⁺ (2) Species[이미지참조] 58

Ⅱ-2-4. Kinetic Measurements and Product Analysis 58

Ⅱ-3. Results and Discussion 60

Ⅱ-3-1. Generation of [FeIV(O)(13-TMC)]²⁺ (2)[이미지참조] 60

Ⅱ-4. Reactivity of [FeIV(O)(13-TMC)]²⁺ (2)[이미지참조] 64

Ⅱ-4-1. Oxidation of Naphthalene Derivatives by [FeIV(O)(13-TMC)]²⁺ (2)[이미지참조] 64

Ⅱ-5. Conclusion 77

Ⅱ-6. References 78

General Conclusion 80

국문 초록 81

Chapter Ⅱ 15

Table Ⅱ-1. Hammett constants (σp) of p-substituted naphthalene, 2nd-order rate constants (k₂) in the oxidation of p-substituted naphthalenes by 2 in MeCN at -20 ℃.[이미지참조] 69

Chapter Ⅰ 8

Figure Ⅰ-1. UV-vis spectral change for the formation of 1 (red line) observed in the reaction of [FeII(13-TMC)]2+ (1.0 mM) with H₂O₂ (10 mM) in the presence of TEA (5.0 mM) in...[이미지참조] 32

Figure Ⅰ-2. UV-vis spectral change for the natural decay of 1 (1.0 mM) in TFE at -10 ℃. Inset shows time trace monitored at 705 nm due to the natural decay of 1. The rate constant... 33

Figure Ⅰ-3. Positive mode CSI-MS spectrum of 1 (1.0 mM) in TFE. The peak at m/z＝330.1 corresponds to [FeIII(13-TMC)(16O2)]2+. Insets show the observed isotope distribution...[이미지참조] 34

Figure Ⅰ-4. X-band EPR spectrum of 1 recorded in TFE at 5 K. 35

Figure Ⅰ-5. Frozen rRaman spectra (λex＝785 nm) of 1-¹⁶O₂ (16 mM; black) and 1-¹⁸O₂ (16 mM; red) in Acetone Blue shows the difference....[이미지참조] 36

Figure Ⅰ-6. UV-vis spectral change observed in the oxidation of PhCHO (4.0 x 10² mM) by 1 (1.0 mM, red line) in TFE at -10 ℃. Inset shows the time profile monitored at 705 nm. 39

Figure Ⅰ-7. Plots of the pseudo-first-order rate constants (kobs) versus concentration of PhCHO in the oxidation of PhCHO-α-h (red circles) and PhCHO-α-d (blue circles) by 1 in...[이미지참조] 40

Figure Ⅰ-8. Plots of Arobs versus concentration of PhCHO derivatives [(a) p-MeO-PhCHO, (b) p-Me-PhCHO, (c) p-Cl-PhCHO, and (d) p-NO₂-PhCHO] for the oxidation of PhCHO... 41

Figure Ⅰ-9. Plot of log(k₂) versus the σₚ⁺ values of p-X-substituted PhCHO derivatives (X＝OMe, Me, H, Cl, and NO₂) for the oxidation of p-X-substituted PhCHO derivatives by 1... 42

Figure Ⅰ-10. Plot of log(k₂) versus the calculated C(O)-H BDE values of substrates for the oxidation of PhCHO derivatives by 1 in TFE at -10 ℃. The calculated C(O)-H BDE values... 43

Figure Ⅰ-11. HPLC chromatograms of (a) the mixed solution of benzoic acid (1.0 mM) and PhCHO (1.0 mM) as an authentic reference and (b) the 10-times diluted reaction solution... 44

Figure Ⅰ-12. 77 K X-band EPR spectra of 1 (1.0 mM, black line) and the complete reaction solution (red line) obtained in the oxidation of PhCHO (5.0 x 10² mM) by 1 (1.0 mM) in... 45

Figure Ⅰ-13. (a) UV-vis spectral change observed in the oxidation of 9,10-dihydroanthracene (40 mM) by 1 (1.0 mM, red line) in TFE:MC (v/v 3:1) at -10 ℃. Inset... 47

Figure Ⅰ-14. (a) UV-vis absorption spectral change observed in the oxidation of 9,10-dihydroanthracene (60 mM) by 1 (1.0 mM, red line) under argon atmosphere in TFE:MC... 48

Figure Ⅰ-15. (a) ESI-MS spectrum of the complete reaction solution obtained in the oxidation of 9,10-dihydroanthracene (60 mM) by 1 (1.0 mM) under argon atmosphere in... 49

Chapter Ⅱ 12

Figure Ⅱ-1. UV-vis absorption spectral change for the formation of 2 by reacting 1 (0.50 mM) and PhIO (2.0 equiv.) in MeCN at -20 ℃. Inset shows time profile monitored at 735... 61

Figure Ⅱ-2. UV-vis absorption spectral change showing the natural decay of 2 (0.50 mM) in MeCN at -20 ℃. Inset shows the time trace monitored at 735 nm due to the natural... 62

Figure Ⅱ-3. 5 K CW-EPR spectrum of 2 (1.0 mM). 63

Figure Ⅱ-4. UV-vis absorption spectral change observed in the oxidation of naphthalene (25 equiv.) by [FeIV(O)(13-TMC)]2+ (0.50 mM; red line) in MeCN at -20 ℃. Inset shows...[이미지참조] 66

Figure Ⅱ-5. Plots of kobs versus concentration of naphthalene-h₈ (black circles) and naphthalene-d₈ (red circles) for the oxidation of naphthalene by 2 in MeCN at -20 ℃ to...[이미지참조] 67

Figure Ⅱ-6. Plots of pseudo-first-order rate constant (kobs) versus concentration of substrates [(a) 1 -bromonaphthalene, (b) 1-chloronaphthalene, (c) 1-methylnaphthalene] for...[이미지참조] 68

Figure Ⅱ-7. Plot of log k₂ versus the σₚ values for the oxidation of naphthalene derivatives by 2 in MeCN at -20 ℃. 70

Figure Ⅱ-8. 5 K EPR spectrum of the complete reaction solution obtained in the oxidation of naphthalene (25 mM) by 2 (0.50 mM) in MeCN at -20 ℃. 71

Figure Ⅱ-9. ESI-MS spectrum of the complete reaction solution obtained in the oxidation of naphthalene (2.5 mM) by 2 (0.50 mM) in MeCN at -20 ℃. The peaks with m/z at 157.6,... 72

Figure Ⅱ-10. GC-MS spectra of (a) 1,4-naphthoquinone (0.50 mM) as an authentic reference and (b) the complete reaction solution obtained in the oxidation of naphthalene... 73

Figure Ⅱ-11. ¹H NMR spectra of (a) 1,4-naphthoquinone (2.0 mM) and (b) naphthalene (2.0 mM) as authentic references, and (c) the complete reaction solution obtained in the... 74

Figure Ⅱ-12. GC-MS spectra of (a) 1,4-naphthoquinone (2.0 mM) as an authentic reference and (b) the complete reaction solution obtained in the oxidation of naphthalene... 75

Chapter Ⅰ 7

Scheme Ⅰ-1. DFT-optimized geometry together with physicochemical properties of a novel Fe(III)-peroxo intermediate bearing a 13-TMC ligand, [FeIII(O₂)(13-TMC)]+ (1)[이미지참조] 26

Scheme Ⅰ-2. Reaction Pathways for the oxidation of an aldehyde by 1: HAT versus NA. 38

Chapter Ⅱ 7

Scheme Ⅱ-1. Proposed mechanism for the hydroxylation of naphthalene by 2. 76

 이 학위 논문은 두 가지 주제로 구성되어 있다: (1) 13-TMC 리간드를 가진 철(III)-퍼옥소 중간체의 친전자성 반응성에 대한 연구 및 (2) 13-TMC 리간드를 가진 철(IV)-옥소 중간체에 의한 방향족 히드록실화에 대한 연구. 첫째, 새로운 철(III)-퍼옥소 중간체([FeIII(O₂)(13-TMC)]+)를 합성하고 CSI-MS, EPR 및 rRaman 분광법을 사용하여 그 분광학적 특성을 규명하였다. 새로운 철(III)-퍼옥소 중간체의 분광학적 특성 규명을 통하여 본 중간체가 O₂-리간드가 배위된 고-스핀 S ＝ 5/2 철(III) 종임을 밝혀내었다. 본 연구 결과는 세계 최초로 처음으로 단핵 비헴철(III)-퍼옥소 종에 의한 산화 반응에서 전례 없는 친전자성 반응성을 보여주고 있다는 사실이다. 둘째, 13-TMC 리간드를 가진 철(IV)-옥소 중간체의 나프탈렌의 산화반응에 대한 반응성을 조사하였다. 13-TMC 리간드를 가진 철(IV)-옥소 중간체는 나프탈렌 유도체를 산화시킬 수 있는 반응성이 높은 산화제임을 확인하였고, 이 때 나프탈렌으로부터 철(IV)-옥소 중간체로의 전자 전달 과정이 속도 결정 단계임을 알 수 있었다.