Title Page
Contents
I. INTRODUCTION 11
1. Unsymmetrical N,N,N-Terdentates 11
1) Synthesis of N,N,N-Terdentates 14
2) Synthesis of Unsymmetrical N,N,N-Terdentates 17
2. N,N,C-Terdentates 19
3) Mechanism of Cyclometallation 23
4) Synthetic Methods for Cyclometallated Complexes 24
II. OBJECTIVES OF RESEARCH 25
III. EXPERIMENTAL 27
1. Synthesis of Ligands 27
2. Synthesis of Cycloplatinated Complexes. 37
3. Synthesis of Ruthenium(Ill) Complexes 39
4. Synthesis of Mixed Ruthenium(Il) Complexes 41
5. Biological Assay 44
6. X-ray Structure Analysis of 10e 44
IV. RESULTS AND DICUSSION 47
1. Synthesis of Unsymmetrical N,N,N-Terdentates 47
1) 2,2'-Bipyridine Realted Unsymmetrical N,N,N-Terdentates 47
2) 1,10-Phenanthroline Realted Unsymmetrical N,N,N-Terdentates 48
2. Synthesis of N,N,C-terdentates 50
1) Annelated Derivative of 6-(2'-Pyridyl)-2-phenylpyridine 50
2) 6-Aryl-2,2'-bipyridines 51
3) Modification of Synthetic Method 52
4) 1,10-Phenanthroline-Related Unsymmetrical N,N,C-Terdentates. 53
3. Properties of Ligands 54
1) Unsymmetrical N,N,N-Terdentates 54
2) N,N,C-Terdentates 56
4. Synthesis and Properties of Cycloplatinated Complexes 69
1) Synthesis and Properties 69
5. Synthesis of Ru(L-N,N',N")Cl₃ and Their Cytotoxicity 74
6. Mixed Complexes of N,N,C-Terdentates with Ru(tpy)Cl₃ 77
1) Synthesis and Properties 77
2) Electronic Properties 83
V. CONCLUSIONS 86
VI. REFERENCES AND NOTES 89
國文草綠 98
英文要約 102
Table 1. Crystallographic data of N,N,C-terdentate 10e 46
Table 2. Properties of 6-Aryl-2,2'-bipyridines 53
Table 3. Selected ¹H NMR Spectral Data of 3,2'-polymethylene-6-(2"-pyridyl)-2-phenylpyridines (10) in CDCl₃. 57
Table 4. Estimated dihedral angles and energy barriers between the two enantiomers 60
Table 5. UV Absorption Spectral Data of 3,2'-Polymethylene-6-(2"-pyridyl)-2-phenylpyridine (10) in 95% EtOH 61
Table 6. Atomic Coordinates [ x 10⁴] and Equivalent Isotropic Displacement Parameters [Å x 10³]. U(eq) is defined as one third of... 65
Table 7. Bond Length [Å] and Angles [°] 66
Table 8. Anisotropic Displacement Parameters [Ų x 10³]. The anisotropic displacement factor exponent takes the form:... 67
Table 9. Torsion Angles (Å) 68
Table 10. Selected ¹H NMR Spectral Data of Cycloplatinated Complexes 33 and 34 in CDCl₃. 72
Table 11. UV Absorption Spectral Data of Cycloplatinated Complexes 33 in DMSO 73
Table 12. In Vitro Cytotoxicity of Ru(L-N,N',N")Cl₃, Antimycin, Cisplatin and Carboplatin in Cell Lines 76
Table 13. ¹H NMR spetroscopic data for [Ru(tpy)(10d-N,N')CI](PF6) (35) in CD₃CN (aromatic region only). 82
Table 14. UV Absorption Spectral Data of Ru(II) Complexes 35 and 36 in CH₃CN 85
Figure 1. Enantiomers of tris(phenanthroline)ruthenium(Il) 12
Figure 2. Schematic view of the enantiomers of Ru(L)32+, where L is a bidentate bound to B-DNA, illustrating the basis of the steroselectivity.[이미지참조] 12
Figure 3. Reaction pattern of Ru(tpy)Cl₃ with ligand 10a. 21
Figure 4. Computer generated structure of [Ru(Il)(tpy)(10a-N,N')CI]CI. 22
Figure 5. Double quantum COSY NMR spectrum of the aromatic region of ligand 10e. 56
Figure 6. Aliphatic region of 10d,e ¹H NMR spectra. 58
Figure 7. Conformational enantiomerism in compounds 10e . 59
Figure 8. An ORTEP drawing of C20H18N2 with the atomic numbering scheme. Hydrogen atoms are omitted for clarity.[이미지참조] 62
Figure 9. An ORTEP drawing of 10e (side view) 63
Figure 10. Stereoscopic representation of C20H18N2[이미지참조] 69
Figure 11. 300 MHz ¹H NMR Spectra of 3,2'-Tetramethylene-6-(2"-pyridyl)-2-phenylpyridine (10e, top) and its Cycloplatinated Complex (33e,... 71
Figure 12. 500 MHz ¹H NMR spectrum of [Ru(tpy)(10d-N,N")Cl](PF6) (35) in CD₃CN.[이미지참조] 80
Figure 13. The double quantum COSY spectrum of [Ru(tpy)(10d-N,N')CI](PF6) (35) in CD₃CN (δ 5.8 -10.5 region).[이미지참조] 81
Figure 14. UV Absorption Spectrum of [Ru(tpy)(10-N,N')Cl]+ and [Ru(tpy)(10e-N,N',C)]+[이미지참조] 84