Title Page
Contents
ABSTRACT IN KOREAN 12
CHAPTER Ⅰ. NTRODUCTION 14
CHAPTER Ⅱ. EXPERIMENT 19
2.1. Materials 19
2.2. Instrumentation 20
2.3. Synthesis of N3PPh₃ Ligand 22
2.4. Synthesis and Characterization of [Fe(N3PPh₃)]³⁺ Complex 23
2.5. Generation and Characterization of [Fe(N3PPh₃)(SA)]²⁺ (1) Complex 24
2.6. Generation and Characterization of Iron(III)-Hydroperoxo (2) Complex 25
2.7. X-Ray Structural Analysis 26
CHAPTER Ⅲ. RESULTS AND DISCUSSION 27
3.1. Synthesis and Characterization of [Fe(N3PPh₃)]³⁺, [Fe(N3PPh₃)(SA)]²⁺ (1), and [Fe(OOH)(N3PPh₃)(SA)]²⁺ (2) Complex 27
3.2. Oxygen Atom Transfer Reactivity of 2 39
3.3. O-H Bond Activation Reactivity of 2 49
3.4. Nucleophilic Reactivity of 2 56
CHAPTER Ⅳ. SUMMARY AND CONCLUSION 60
CHAPTER Ⅴ. REFERENCES 61
Abstract 64
Table 1. Crystallographic data and refinements for [Cu(N3PPh₃)(CH₃CN)]³⁺ 16
Table 2. Selected bond distances (Å) and angles (°) for [Cu(N3PPh₃)(CH₃CN)]³⁺ 17
Table 3. Bond distances and angles of DFT-optimized structure of [FeIII(OOH)(N3PPh₃)(SA)]²⁺(2)[이미지참조] 38
Figure 1.1. Synthetic scheme of [Fe(N3PPh₃)]³⁺, [Fe(N3PPh₃)(SA)]²⁺, and [FeIII(OOH)(N3PPh₃)(SA)]²⁺ complex[이미지참조] 18
Figure 3.1. UV-vis spectral changes obtained in the reaction between [Fe(N3PPh₃)]³⁺ (0.50 mM, black line) and sodium salicylate (1.0 mM, blue line) in CH₃CN at room temperature. 29
Figure 3.2. UV-vis spectral changes obtained in the reaction between [Fe(N3PPh₃)]³⁺ (0.50 mM, black line) and sodium salicylate (1.0 mM, blue line) in CH₃CN at room temperature.... 30
Figure 3.3. ESI-MS spectrum of 1. The peaks at m/z=347.6 and 830.9 correspond to [Fe(N3PPh₃)(SA)]²⁺ (calculated m/z=347.6) and {[FeIII(N3PPh₃)(SA)](SA⁻)}⁺ (calculated...[이미지참조] 31
Figure 3.4. Overlaid ATR FT-IR spectra of the [Fe(N3PPh₃)]³⁺ (black line), 1 (red line), and sodium salicylate (blue line). The spectra were recorded from solid samples deposited... 32
Figure 3.5. Overlaid cyclic voltammograms of 1 in CH₃CN with a glassy carbon working electrode at 20 ℃. 33
Figure 3.6. UV-vis spectral changes of 2 obtained in the reaction between 1 (0.50 mM, blue line) with perchloric acid (0.50 mM, red line) in CH₃CN at room temperature. 34
Figure 3.7. X-band electron paramagnetic resonance (EPR) spectrum 2 in frozen CH₃CN at 80 K. 35
Figure 3.8. Overlaid ATR FT-IR spectra of the 2 (black line) and [Fe(OOD)(N3PPh₃)(SA)]²⁺ (red line). The spectra were recorded from solution samples... 36
Figure 3.9. DFT-optimized structure for 2 via B3LYP/6-31G(d,p). Atom colors: Fe, navy; N, blue; O, red; P, purple; C, grey; H, white. 37
Figure 3.10. UV-vis spectral changes obtained in the reaction between 2 (0.50 mM) and triphenylphosphine (5.0 mM) in CH₃CN at room temperature. 41
Figure 3.11. Plot of kobs against the concentrations of triphenylphosphine obtained in the reaction between 2 (0.50 mM) and substrates in CH₃CN at room temperature.[이미지참조] 42
Figure 3.12. UV-vis spectral changes obtained in the reaction between 2 (0.50 mM) and thioanisole (100 mM) in CH₃CN at room temperature. 43
Figure 3.13. UV-vis spectral changes obtained in the reaction between 2 (0.50 mM) and 4- nitrothioanisole (25 mM) in CH₃CN at room temperature. 44
Figure 3.14. Proposed mechanisms of oxygen atom transfer reactions by 2 45
Figure 3.15. Hammett plot obtained in the reaction between 2 and para-X-thioanisole (X=OMe, Me, H, F, Br, CN, and NO₂) in CH₃CN at room temperature. 46
Figure 3.16. Plot of kobs against the concentrations of 4-methoxythioanisole, 4- methylthioanisole, thioanisole, 4-fluorothioanisole, 4-bromothioanisole, 4-...[이미지참조] 48
Figure 3.17. UV-vis spectral changes obtained in the reaction between 2 (0.10 mM) and 2,6-di-tert-butyl-4-methylphenol (2.0 mM) in CH₃CN at room temperature. 51
Figure 3.18. Plot of kobs against the concentrations of 2,6-di-tert-butyl-4-methoxyphenol, 2,6-di-tert-butyl-4-methylphenol, 2,4,6-tri-tert-butylphenol, 2,6-di-tert-butylphenol, and...[이미지참조] 53
Figure 3.19. O-H bond activation Hammett Plot of logk₂ against (a) σρ⁺, (b) O-H bond dissociation energy, (c) pKa, and (d) E ₁/₂ of 2,6-di-tert-butyl-p-X-phenol (X=OMe, Me,...[이미지참조] 54
Figure 3.20. Proposed mechanisms of O-H bond activation reactions by 2 55
Figure 3.21. UV-vis spectral changes obtained in the reaction between 2 (0.50 mM) and benzoyl chloride (100 mM) in CH₃CN at room temperature. 57
Figure 3.22. Plot of kobs against the concentrations of benzoyl chloride obtained in the reaction between 2 (0.50 mM) and substrates in CH₃CN at room temperature.[이미지참조] 58
Figure 3.23. UV-vis spectral changes obtained in the reaction between 2 (0.50 mM) and 2- phenylpropionaldehyde (50 mM) in CH₃CN at room temperature (left panel). Plot of kobs...[이미지참조] 59