Oxidative Addition of Me-I and Me-Re Bonds on Organoplatinum(II) Complexes

توضیحات

Oxidative Addition of Me-I and Me-Re Bonds on Organoplatinum(II) Complexes

تعداد129 صفحه در فایل word

Ph.D. Dissertation In Inorganic Chemistry

Oxidative Addition of Me-I and Me-Re Bonds on Organoplatinum(II) Complexes

Abstract

Keywords: Organoplatinum Compounds, Oxidative Addition Reaction.

Table of Contents

List of Figures

Figure A.1.1. Some common ligands for cyclometallation 9

Figure A.1.2. Mechanisms of cyclometallation reactions 10

Figure A.3.1. 1H NMR spectrum (250 MHz) of [Me2Pt(m-SMe2)2PtMe2] in CDCl3 26

Figure A.3.2. 1H NMR spectrum (250 MHz) of [PtMe2(dmso)2] in CDCl3 28

Figure A.3.3. 1H NMR spectrum (250 MHz) of [Pt(Me)(tpy)(dmso)], in CDCl3 30

Figure A.3.4.1H NMR spectrum (250 MHz) of [Pt(Me)(tpy)( PPh3)], in CDCl3 33

Figure A.3.5. 31P NMR spectrum (202 MHz) of [Pt(Me)(tpy)( PPh3)], in CDCl3 34

Figure A.3.6. 1H NMR spectrum (250 MHz) of [Pt(Me)(tpy)( PMePh2)], in CDCl3 35

FigureA.3.6.1. Expansion of aliphatic region of 1H NMR spectrum (250 MHz) of [Pt(Me)(tpy)(PMePh2)], in CDCl3.. 36

Figure A.3.7. 31P NMR spectrum (202 MHz) of [Pt(Me)(tpy)(PMePh2)], in CDCl3 37

Figure A.3.8. 1H NMR spectrum (250 MHz) of [PtMe2I(tpy)( PPh3)], in C6D6. 41

Figure A.3.9. 31P NMR spectrum (202 MHz) of [PtMe2I(tpy)( PPh3)], in CDCl3 42

Figure A.3.8. 1H NMR spectrum (400MHz) of [PtMe2I(tpy)(PPh2Me)], in CDCl3 43

Figure A.3.11. 31P NMR spectrum (162 MHz) of [PtMe2I(tpy)(PMePh2)], in CDCl3 44

Figure A.3.12. Plots showing correlations between the 1JPtP values with Pt charge in complexes 1 (top) and the Pt-P bond lengths (Å) in complexes 3(down) 48

Figure A.3.13. Changes in the UV-visible spectrum during the reaction of [PtMe(tpy)PPh3], (1.0×10-4 M) with MeI (0.81 mmol) in CHCl3 at T = 25 ˚C, successive spectra was recorded at intervals of 1 min 50

Figure A.3.14. Absorbance-time curves for the reaction of [PtMe(tpy)PPh3], with MeI (0.96, 1.28, 1.61, 1.93, 2.25 mmol); [MeI] increases reading downward) in CHCl3 at T = 25˚C 51

Figure A.3.15. Plots of first-order rate constants (kobs/s-1) for the reaction of [PtMe(tpy)(PMePh2)], with MeI in CHCl3 at different temperatures versus concentration of MeI 52

Figure A.3.16. Eyring plots for the reaction of (a) [PtMe(tpy)PPh3] + MeI and (b) [PtMe(tpy)(PMePh2)] + MeI in CHCl3 53

Figure A.3.17. Calculated structures and relative energies of starting materials (1c + MeI), potential intermediates (M and N) and products of oxidative addition (2c and 3c) in acetone solvent. The H atoms are omitted for more clarity 56

Figure B.1.1. Oxo bridge Ni/Cu complex containing nucleophilic oxo groups 78

Figure B.3.1. 1H NMR Spectrum (250 MHz) of [PtMe2(bipy)], in CDCl3 91

Figure B.3.2. 1H NMR Spectrum (250 MHz) of [Pt(p-MeC6H4)2(bipy)], in CDCl3 93

Figure B.3.3. 1H NMR Spectrum (250 MHz) of [PtMe2(dppe)], in CDCl3. 94

Figure B.3.4. 1H NMR Spectrum (250 MHz) of MeReO3, in CDCl3 96

Figure B.3.5. 1H NMR Spectrum (250 MHz) of [(bipy)Me3Pt(μ–O)ReO3], in CDCl3. 98

Figure B.3.6. 13C NMR Spectrum (100 MHz) of [(bipy)Me3Pt(μ–O)ReO3], in CD2Cl2 99

Figure B.3.6.1. 13C NMR Spectrum of [(bipy)Me3Pt(μ–O)ReO3], in CD2Cl2. Expansion of aromatic region. 100

Figure B.3.7. 195Pt NMR Spectrum (86 MHz) of [(bipy)Me3Pt(μ–O)ReO3], in CD2Cl2 101

Figure B.3.8. X-ray crystal structures of molecular structure of [(bipy)Me3Pt(μ–O)ReO3]. Hydrogen atoms have been omitted for clarity. Selected bond length (Å) and angle (°) 104

Figure B.3.10. Calculated structures and energies of intermediates and compounds in the reaction of MTO with [PtMe2(bipy)] in benzene 109

Figure B.3.11. Qualitative frontier molecular orbitals and the relative compositions of the different energy levels in terms of composing fragments for complex [(bipy)Me3Pt(μ–O)ReO3] 110

List of Table

Figure A.3.1.¹H NMR spectrum (250 MHz) of [Me₂Pt(m-SMe₂)₂PtMe₂] in CDCl₃ 26

Figure A.3.2.¹H NMR spectrum (250 MHz) of [PtMe₂(dmso)₂] in CDCl₃ 28

Figure A.3.3. ¹H NMR spectrum (250 MHz) of [Pt(Me)(tpy)(dmso)], in CDCl₃30

Figure A.3.4.¹H NMR spectrum (250 MHz) of [Pt(Me)(tpy)( PPh₃)], in CDCl₃ 33

Figure A.3.5. ³¹P NMR spectrum (202 MHz) of [Pt(Me)(tpy)( PPh₃)], in CDCl₃ 34

Figure A.3.6. ¹H NMR spectrum (250 MHz) of [Pt(Me)(tpy)( PMePh₂)], in CDCl₃ 35

FigureA.3.6.1. Expansion of aliphatic region of¹H NMR spectrum (250 MHz) of [Pt(Me)(tpy)(PMePh₂)], in CDCl_3.. 36

Figure A.3.7.³¹P NMR spectrum (202 MHz) of [Pt(Me)(tpy)(PMePh₂)], in CDCl₃ 37

Figure A.3.8. ¹H NMR spectrum (250 MHz) of [PtMe₂I(tpy)( PPh₃)], in C₆D_6. 41

Figure A.3.9. ³¹P NMR spectrum (202 MHz) of [PtMe₂I(tpy)( PPh₃)], in CDCl₃42

Figure A.3.8. ¹H NMR spectrum (400MHz) of [PtMe₂I(tpy)(PPh₂Me)], in CDCl₃ 43

Figure A.3.11. ³¹P NMR spectrum (162 MHz) of [PtMe₂I(tpy)(PMePh₂)], in CDCl₃ 44

Figure A.3.12. Plots showing correlations between the ¹J_PtP values with Pt charge in complexes 1 (top) and the Pt-P bond lengths (Å) in complexes 3(down) 48

Figure A.3.13. Changes in the UV-visible spectrum during the reaction of [PtMe(tpy)PPh₃], (1.0×10^-4M) with MeI (0.81 mmol) in CHCl₃ at T = 25 ˚C, successive spectra was recorded at intervals of 1 min 50

Figure A.3.14. Absorbance-time curves for the reaction of [PtMe(tpy)PPh₃], with MeI (0.96, 1.28, 1.61, 1.93, 2.25 mmol); [MeI] increases reading downward) in CHCl₃ at T = 25˚C 51

Figure A.3.15. Plots of first-order rate constants (k_obs/s^-1) for the reaction of [PtMe(tpy)(PMePh₂)], with MeI in CHCl₃ at different temperatures versus concentration of MeI 52

Figure A.3.16. Eyring plots for the reaction of (a) [PtMe(tpy)PPh₃] + MeI and (b) [PtMe(tpy)(PMePh₂)] + MeI in CHCl₃ 53

Figure B.3.1. ¹H NMR Spectrum (250 MHz) of [PtMe₂(bipy)], in CDCl₃ 91

Figure B.3.2. ¹H NMR Spectrum (250 MHz) of [Pt(p-MeC₆H₄)₂(bipy)], in CDCl₃93

Figure B.3.3. ¹H NMR Spectrum (250 MHz) of [PtMe₂(dppe)], in CDCl₃. 94

Figure B.3.4. ¹H NMR Spectrum (250 MHz) of MeReO₃, in CDCl₃ 96

Figure B.3.5.¹H NMR Spectrum (250 MHz) of [(bipy)Me₃Pt(μ–O)ReO₃], in CDCl₃. 98

Figure B.3.6.¹³C NMR Spectrum (100 MHz) of [(bipy)Me₃Pt(μ–O)ReO₃], in CD₂Cl₂ 99

Figure B.3.6.1.¹³C NMR Spectrum of [(bipy)Me₃Pt(μ–O)ReO₃], in CD₂Cl₂. Expansion of aromatic region. 100

Figure B.3.7. ¹⁹⁵Pt NMR Spectrum (86 MHz) of [(bipy)Me₃Pt(μ–O)ReO₃], in CD₂Cl₂ 101

Figure B.3.8. X-ray crystal structures of molecular structure of [(bipy)Me₃Pt(μ–O)ReO₃]. Hydrogen atoms have been omitted for clarity. Selected bond length (Å) and angle (°) 104

Figure B.3.10. Calculated structures and energies of intermediates and compounds in the reaction of MTO with [PtMe₂(bipy)] in benzene 109

Figure B.3.11. Qualitative frontier molecular orbitals and the relative compositions of the different energy levels in terms of composing fragments for complex [(bipy)Me₃Pt(μ–O)ReO₃] 110