Dissertations / Theses on the topic 'Osmium compounds. Ruthenium compounds. Porphyrins'

This thesis work reports developments in the coordination chemistry of ruthenium porphyrin complexes, both in terms of the synthesis and chemistry of new compounds, as well as the study of the solution chemistry of some previously reported complexes. The synthesis, characterization and chemistry of ten new Ru(porp) coordination complexes in the oxidation states Ru[superscript]Ⅲ and Ru[superscript]Ⅳ containing halide (Br, CI) and other axial ligands (pyridine, CH₃CN, NH₃ and SbF₆) are described in this thesis. Some additional ten Ru(porp) complexes have been studied in situ. Measurement of the rate constants for forward and reverse reactions and the corresponding equilibrium constant by 'H NMR and UV/visible spectroscopy for the dissociation of PPh₃ ligand from Ru(OEP)L(PPh₃) (OEP is the octaethylporphyrinato dianion; L = CO, PPh₃) in C₇D₈ to generate the previously reported five-coordinate Ru(OEP)L complexes allowed for an estimation of the Ru-P bond strength (64 ± 9 kJ mol⁻¹) in these complexes. A study of PPh₃ dissociation from Ru(OEP)CO(PPh₃) in C₇D₈ and in CDC1₃ indicates that solvation effects play a major role, with CDC1₃ being more capable than C₇D₈ of solvating the Ru(OEP)CO complex. The presence of trace H₂0 in these systems was a major problem, and the coordination of H₂0 to Ru(OEP)L complexes to generate the in situ Ru(OEP)L(H₂0) complexes (L = CO, PPh₃) is described. The formation of Ru(OEP)L(H₂0) and the observed difference in the solvation of Ru(OEP)CO by C₇H₈ and CHC1₃ indicate that truly Five-coordinate species may not exist in solution. The outer-sphere oxidation of Ru [superscript]Ⅳ(OEP)PPh₃ by 0₂ to give [Ru [superscript]Ⅳ(OEP)OH]₂0 was shown to occur only in the presence of H₂0. Mechanistic studies on the previously reported reaction of HCI with [Ru(OEP)]₂ to generate Ru^(OEP)Cl₂ (C. Sishta, M.Sc.Thesis, University of British Columbia, 1986) show that solvent plays a major role in directing this oxidation reaction. A reaction stoichiometry of 4:1 between HCI and [Ru(OEP)]₂ in C₆D₆ or C₇D₈ showed that HCI itself was the oxidant and not trace Cl₂ in HCI, as thought previously. A range of HX acids having pK[subscript]a, values in the range 38 to less than -10 (HX = H₂, MeOH, H₂0, H₂S, CH₃COOH, C₆H₅COOH, HF, CF₃COOH, HN0₃, HBF₄, HCI. HBr, and HSbF₆) were tested for reactivity with [Ru(OEP)]₂in C₆D₆; the data showed that a strong acid (pK[subscript]a < ca. 0) was necessary to initiate reactivity. The complex Ru[superscript]Ⅳ(OEP)(SbF₆)₂ was generated in situ by reacting HSbF₆ with [Ru(OEP)]₂. In CH₂C1₂, a 1:1 stoichiometric reaction between HCI and [Ru(OEP)]₂ was observed, instantly fanning a mixture of products, tentatively formulated as Rura(OEP)H and [Ru[superscript]Ⅲ(OEP)]₂CHCl₂ based on spectroscopic data. The species proved impossible to separate. These same products were formed slowly by the reaction of [Ru(OEP)]₂ with CH₂C1₂ in the absence of HCI, and kinetic studies suggest that a direct reaction of [Ru(OEP)]₂ with CH₂C1₂ is likely, rather than reaction of [Ru(OEP)]₂ with impurities in CH₂C1₂. The product mixture generated Ru(OEP)Cl₂ upon further reaction with HCI, both in the absence and in the presence of air. The complex Ru[superscript]Ⅳ(OEP)(BF₄)₂ was generated in situ by an analogous reaction of aqueous HBF₄ with the product mixture. The required hydrogen-containing co-product from the reaction of HX (X = Br, CI) with [Ru(OEP)|₂ in C₇D₈ or CH₂C1₂ was not detected, but was shown not to be H₂. Oxidation of Ru(porp)(CH₃CN)₂ and Ru(OEP)py₂ (py = pyridine; porp = OEP, TMP (the dianion of tetramesitylporphyrin)) by gaseous HX (X = Br, CI) in the absence of air yielded Ru[superscript]Ⅳ(porp)X₂ complexes. The new compound Ru(TMP)Br₂ was synthesized by this method using the bis(acetonitrile) precursor, and was characterized by spectroscopy; the chloride analogue Ru(TMP)Cl₂ was generated in situ. The magnetic properties (susceptibility and moment) of Ru(OEP)Br₂ from 6 to 300 K are unlike those reported for ruthenium(IV) non-porphyrin complexes, and reveal a significant contribution from temperature-independent paramagnetism. The reaction of Ru(OEP)X₂ (X = Br, CI) with NH₃ gave the complexes Ru[superscript]Ⅲ(OEP)X(NH₃), which upon acidification under an inert atmosphere yielded the Rum(OEP)X compounds. These Ru111 complexes were characterized by spectroscopic techniques, and the solution chemistry of the five-coordinate species Ru(OEP)X was developed: the Ru[superscript]Ⅲ(OEP)X(CH₃CN) species were also characterized. Solvation of the five-coordinate species Ru(OEP)X (X = Br, CI) was observed in coordinating solvents to form the six-coordinate species Ru(OEP)X(solvent) (solvent = py, CH₃CN and MeOH). Estimates of the equilibrium constants for the association of these ligands to Ru(OEP)X were obtained from UV/visible titration experiments in CH₂C1₂. Similarly, the equilibrium constant for the association of Br to Ru(OEP)Br to generate in situ (n-Bu)₄N⁺[Ru[superscript]Ⅲ(OEP)Br⁺₂]", was measured. Disappointingly, the complexes Ru(OEP)X were shown not to catalyze the oxidation of organic substrates such as cyclohexene. Electrochemical and spectroelectrochemical studies of the complexes Ru(OEP)X₂ and Ru(OEP)X (X = Br, CI) showed that the Ru[superscript]Ⅳ/Ru[superscript]Ⅲ couple occurred at 480-460 mV and 950-870 mV vs. NHE, respectively, and that the probable reductant for the reaction of Ru(OEP)X₂ with NH₃ was NH₃ itself. A facile reduction of Ru(OEP)(SbF₆)₂ gave the complex Ru[superscript]Ⅲ(OEP)SbF₆, by a probable homolysis of the Ru-F bond. The outer-sphere oxidation of Ru(OEP)py₂ by air in the presence of HX acids gave the isolated or in situ characterized complexes [Ruin(OEP)py₂]+ X" (X = CI, Br, F, BF₄). Similar oxidation of Ru(OEP)(CH₃CN)₂ formed [Ru(OEP)(CH₃CN)₂]+ Br-. Electrochenucal studies showed that 0₂ in acidic media was capable of oxidizing the Ru(OEP)(solvent)₂ complexes (solvent = py, CH₃CN) to the Ru[superscript]Ⅲ complexes, presumably generating H0₂ .
Science, Faculty of
Chemistry, Department of
Graduate

The oxidation of three alkyl thioethers, phenol and 2-propanol by trans-dioxo ruthenium porphyrin species, and the synthesis, characterization and reactivity of several new ruthenium porphyrin complexes are described in this thesis. The trans-dioxo species Ru(Porp)(O)₂ [Porp= the dianions of 5,10,15,20-tetramesitylporphyrin (TMP) and 5,10,15,20-(2,6-dichlorophenyl)porphyrin (OCP)] selectively oxidize diethyl-, di-n-butyl- and decylmethyl- sulfides to the corresponding sulfoxides at room temperature. The reaction is first order in [Ru] and in [thioether]. The second order rate constants for the first O-atom transfer from the Ru(TMP) system are: 7.54xl0⁻³, 1.23xl0⁻² and 1.14x10-¹ M⁻¹ s⁻¹ respectively for the three thioethers at 20.0 °C. The activation parameters for the O-atom transfer process are also determined: for Et₂S, ∆H‡= 58.3 kJ mol⁻¹ and ∆S‡= -86 J K⁻¹ mol⁻¹; for nBu₂S, AH‡= 47.4 kJ mol⁻¹and ∆S‡= -120 J K⁻¹ mol⁻¹; for DecMeS, ∆H‡= 56.5 kJ mo⁻¹ and ∆S‡= -70 J K⁻¹ mol⁻¹. A second order rate constant of 7.23xl0⁻²M⁻¹s⁻¹ is measured at 20.0 °C for the oxidation of Et₂S by Ru(OCP)(O)₂. The intermediates Ru(TMP)(OSEt₂)₂, Ru(TMP)(OSEt₂)(OSEt₂) and the final product Ru(TMP)(0SEt₂)₂,where O and S refer to O- and S- bonded sulfoxide, are observed by ¹H nmr, and the last mentioned is isolated and characterized. A mechanism is proposed, based on electrophilic attack of the O=Ru=O moiety on :SR₂ to form bis-O-bonded species which subsequently isomerizes to bis-S-bonded species via mixed species. The Ru(TMP)(O)₂/Et₂S/O₂ system at room temperature is catalytic in complex, but produces only about 5 turnovers due to poisoning of the catalyst by the reaction product. The same system at >65 °C gives higher turnovers, but now porphyrin ligand degradation is observed, perhaps via oxidation by the O=Ru=O moiety. The Ru(OCP)(0)₂/Et₂S/O₂ system at 100 °C catalytically oxidizes Et₂S to Et₂SO and Et₂SO₂ (in ~ 4:1 ratio) and the porphyrin ligand does not undergo oxidative destruction. The Ru(TMP)(O)₂ species reacts with phenol via an observed intermediate Ru(TMP)(p-O(H)C₆H₄OH)₂ to form Ru(IV)(TMP)(OC₆H₄OH)₂, a paramagnetic (S=l) complex which is isolated and characterized. The oxidation reaction is first order in both [Ru] and [phenol] with a second order rate constant 6.90x10⁻² M⁻¹ s⁻¹at 20.0 °C. A mechanism based on electrophilic attack by the O=Ru=O moiety on the aryl ring followed by proton migration is proposed. This mechanism also explains the formation of some free para-benzoquinone and 1 equivalent of water per Ru. No ortho-benzoquinone is formed in the reaction. Preliminary ⁻H nmr studies reveal that 2-propanol is oxidized to acetone by Ru(TMP)(O)₂. A paramagnetic species (S= 1) was isolated as the only porphyrin product but not characterized. A range of novel ruthenium porphyrin complexes is also prepared. The reaction of acetylene with the four-coordinate Ru(TMP) species forms [Ru(TMP)]₂(u-C₂H₂), the first reported organometallic ruthenium porphyrin dimer. The complexes, Ru(TMP)(PhCCPh) and Ru(TMP)(PhCCH), the first π-bonded alkyne species in ruthenium porphyrin chemistry, are characterized in solution. The π-bonded alkene complexes Ru(TMP)(CH₂CH₂) OPrOH).(iPrOH) and Ru(TMP)(CH₂CH₂) are isolated and characterized, while the Ru(TMP)(cyclohexene) complex is characterized in situ. The Ru(TMP)(OSEt₂)₂ complex is isolated also by the reaction of Ru(TMP)(CH₃CN)₂with Et₂SO. The Ru(TMP)(L)₂ complexes, L= OSMe₂, OSnPr₂ and OSnBu₂ are also prepared via the above method and characterized. Some new Ru(OCP) complexes, (the monocarbonyl, the bis-acetonitrile and the dioxo- species) are also isolated and characterized.
Science, Faculty of
Chemistry, Department of
Graduate

Transition metal catalyzed selective nitrene insertion into C-H bonds, which allows direct incorporation of nitrogen functionality into hydrocarbons, represents an appealing methodology for C-N bond formation, a type of bond formation of great importance in organic synthesis due to the prevalence of amino groups in biologically active natural products and pharmaceuticals. Organic azides are atom-economic and an environment-benign nitrene source. This dissertation reports the use of organic azides as a nitrene source to develop a series of protocols for C-H bond functionalization by metal-catalyzed nitrene insertion, including the diimination of indoles, the phosphoramidation of aldehydes and the amination of hydrocarbons catalyzed by ruthenium porphyrins. Carbonylruthenium(II) porphyrin complex Ru(TTP)(CO) (TTP = meso-tetrakis(p-tolyl)porphyrinato dianion) is an effective catalyst for nitrene transfer to sp2 C-H bonds of indoles using aryl azides (ArN3) as a nitrene source. This “Ru(TTP)(CO) + ArN3” protocol selectively results in the diimination of indoles without the corresponding monoimination products being detected. In the presence of a catalyst Ru(TTP)(CO), the reactions of N-methylindole with ArN3 (Ar = 4-nitrophenyl; 3,5-bis(trifluoromethyl)phenyl), and reactions of a variety of N-substituted indoles with 4-nitrophenylazide, afford 2,3-diiminoindoles in good to excellent yields (up to 90%). This unique type of 2,3-diimination products was characterized by NMR spectroscopy, mass spectrometry and single crystal X-ray crystallography. The catalytic diimination product from N-methylindole and ArN3 (Ar = 3,5-bis(trifluoromethyl)phenyl) can also be obtained through stoichiometric reaction of N-methylindole with the corresponding bis(arylimido)ruthenium(VI) porphyrin, suggesting the possible involvement of RuVI(TTP)(NAr)2 intermediates in the Ru(TTP)(CO)-catalyzed diimination reactions. Dichlororuthenium(IV) porphyrin complex Ru(TTP)Cl2 efficiently catalyzes the phosphoramidation of aldehydes with phosphoryl azides (RO)2P(O)N3 via a nitrene insertion into sp2 C-H bonds of aldehydes. This represents the first study on the catalytic activity of a ruthenium(IV) porphyrin towards nitrene insertion into C-H bonds. The “Ru(TTP)Cl2 + (RO)2P(O)N3” protocol exhibits high chemoselectivity and functional group tolerability. Good to excellent product yields (up to 99%) have been obtained for the Ru(TTP)Cl2-catalyzed phosphoramidation of a wide variety of aldehydes with commercially available (PhO)2P(O)N3 (DPPA) and phosphoramidation of p-tolualdehyde with various (RO)2P(O)N3 (R = Me, Et, CCl3CH2, 4-nitrophenyl). The reaction can be scaled up by adding phosphoryl azide dropwise. The use of commercially available DPPA in this protocol offers a convenient and practical method for the synthesis of N-acylphosphoramidates. “Ru(TDCPP)Cl2 + (CCl3CH2O)2P(O)N3” (TDCPP = meso-tetrakis(2,6-dichlorophenyl)porphyrinato dianion) serves as an effective protocol for intermolecular nitrene insertion into sp3 C-H bonds of hydrocarbons. Using this protocol, a variety of hydrocarbons including cycloalkanes (such as cyclohexane) and ethylbenzenes undergo sp3 C-H amination in moderate to high yields (up to 86%). Compared with ruthenium(II) porphyrins such as Ru(TDCPP)(CO) and dirhodium carboxylates such as Rh2(OAc)4, Ru(TDCPP)Cl2 displays a markedly higher catalytic activity towards the nitrene sp3 C-H insertion with (CCl3CH2O)2P(O)N3. In addition, intramolecular nitrene insertion into sp3 C-H bond can also take place in good yields with Ru(TDCPP)Cl2 as the catalyst.
published_or_final_version
Chemistry
Doctoral
Doctor of Philosophy

Le cancer figure parmi les principales causes de décès dans le monde. Afin de traiter le cancer, les chimiothérapies en combinaison avec la chirurgie sont les plus utilisées. Des composés organométalliques tel que les sels de platine représentent une référence en clinique. Malgré leur succès, ils comportent des limites qui sont des toxicités sur les tissus sains et le développement de résistances. Notre équipe collabore depuis plusieurs années avec divers chimistes afin de développer de nouvelles molécules organométalliques anticancéreuses à base de Ruthénium (ROC) et à base d'Osmium (ODC). Au cours de ma thèse, j'ai réalisé des études de type structure/fonction de nouvelles molécules afin de trouver les paramètres physicochimiques importants pour leur activité biologique et afin d'identifier leur mode d'action. Mes travaux ont démontré que le potentiel d'oxydoréduction des composés serait un facteur important pour leur cytotoxicité. De plus, j'ai identifié de nouvelles voies de signalisation régulées par ces composés, tels que les voies de signalisation d'Hif-1 et Nrf2, et les HDAC. L'ensemble de ces résultats nous permet de mieux comprendre les propriétés biologiques des composés organométalliques ce qui à terme devrait permettre une optimisation de leur structure pour améliorer leur activité anticancéreuse
Cancer is one of the leading causes of death in the world. To treat cancer, several therapeutic approaches exist. Chemotherapy in combination with surgery is one of the most used. Organometallic compounds such as platinum salts represent a reference in clinic. Despite their success, they have limitations that are toxicity to healthy tissue and the development of resistance. Our team has been working for several years with chemists to develop new organometallic Ruthenium (ROC) and Osmium compounds (ODC). During my Ph.D. I performed structure/function studies on novel molecules in order to find the important physico chemical parameters for their biological activity. My work demonstrated that the redox potential is a crucial factor for the cytotoxicity of the compounds. ln addition, I identified novel regulatory pathways that are targeted by these compounds, such as the Hif1 and Nrf2 pathways, and the HDACs. All together these results allow us to have a better understanding of the biological properties of the organometallic compounds, which will in time allow a optimization of their structure to favor their anticancer activity

by Lo Tim Lun.
Thesis (M.Phil.)--Chinese University of Hong Kong, 1998.
Includes bibliographical references (leaves 68-71).
Abstract also in Chinese.
Acknowledgments --- p.i
Abstract --- p.ii
Abbreviations --- p.iii
Table of Contents --- p.iv
Chapter Part 1. --- "Arene Oxidation with 2,6-Dichloropyridine- N-oxide Catalyzed by Ruthenium Porphyrins" --- p.1
Chapter 1. --- Introduction --- p.1
Chapter 1.1 --- Natural Occurrence of Cytochrome P-450 --- p.1
Chapter 1.2 --- Biomimetic Models of Cytochromes of P-450 --- p.4
Chapter 1.3 --- Homogenous Metalloporphyin Catalyzed Oxidation Mimicking Cytochrome P-450 --- p.5
Chapter 1.4 --- Synthetic Porphyrin Revolution: Third Generation of Porphyrins --- p.6
Chapter 1.5 --- Fourth-Generation of Porphyrins --- p.9
Chapter 1.6 --- Variation of Oxygen Donors and Bound Transition Metals --- p.11
Chapter 1.7 --- Objective --- p.12
Chapter 2. --- Results and Discussion --- p.15
Chapter 2.1 --- Synthesis of β-tetraaryl Substituted Mesitylporphyrin and their Ruthenium Carbonyl Complexes --- p.15
Chapter 2.2 --- "Oxidation of Aromatic Compounds Catalyzed by Ruthenium Porphyrins in 2,6-Dichloropyridine N-oxide System" --- p.17
Chapter 2.3 --- "Synthesis of trans-Dichloro-tetrakis(p-chlorophenyl)- tetramesitylporphyrinato Ruthenium(IV) Complex, trans- RuTMP(p-ClPh)4(Cl2)" --- p.21
Chapter 2.4 --- "Oxidation of Aromatic Compounds Catalyzed by trans- Ru(TMP)(p-ClPh)4(Cl2) with 2,6-Dichloropyridine N- oxide" --- p.24
Chapter 2.5 --- "Effect of Additives to the Catalytic Oxidation of Aromatic Compound by Ru(por)-2,6-Dichloropyridine N- oxide" --- p.24
Chapter 2.6 --- "Effect of Lewis Acids on the Catalytic Oxidation of Aromatic Compound by Ru(por)-2,6-Dichloropyridine N- oxide" --- p.27
Chapter 3. --- Conclusion --- p.29
Chapter 4. --- Experimental Section --- p.30
Chapter 5. --- Reference --- p.39
Chapter Part 2. --- Imine Complexes of Ruthenium and Manganese with Acyclic Tetradenate N202-Donors as Oxidation Catalysts for Styrene Epoxidation --- p.42
Chapter 1 --- Introduction --- p.42
Chapter 1.1 --- Salen-type Metal Complexes with N202 Anionic Donor Set --- p.43
Chapter 1.2 --- High-valent Ruthenium Complexes with π-Aromatic Imine Ligand --- p.45
Chapter 1.3 --- Objective --- p.47
Chapter 1.3.1 --- Metal Complexes of Phenanthroline-π-aromatized Imlne --- p.47
Chapter 1.3.2 --- Ruthenium Complex of Jacobsen Ligand --- p.48
Chapter 2 --- Results and Discussion --- p.50
Chapter 2.1 --- "Synthesis of cis-Dicarbonyl-[(R,R)-N, N,-bis(3,5-di-tert- butylsalcylidene)-1,2-cyclohexanediaminato (2-)] Ruthenium(II) Complex" --- p.50
Chapter 2.2 --- "Synthesis of 2,9-Bis(3,5-di-tert-butyl-2-hydroxyphenyl)- 1,10-phenanthroline and Its Manganese and Ruthenium Complexes" --- p.55
Chapter 2.3 --- Epoxidation of Styrene Catalyzed by Manganese and Ruthenium Phenanthroline Complexes with Hyprochlorite as Oxidant in Different pH Media --- p.58
Chapter 3. --- Conclusion --- p.60
Chapter 4. --- Experimental Section --- p.61
Chapter 5. --- Reference --- p.69
Appendix --- p.73
NMR Spectra --- p.78

本文主要探討在有水的條件下，分別以銠卟啉和鈷卟啉絡合物與無張酮反應發生選擇羰基碳及α碳(C(CO)-C(α))鍵活化（下稱碳碳鍵活化）的反應活性和反應機。
在200°C，無張芳香和脂肪酮與5, 10, 15, 20-(四甲苯) 銠卟啉絡合物（RhIII(ttp)X，X = Cl 和Me）進反應，生成相對應的碳碳鍵活化產物－銠卟啉酰基絡合物，產最高可達97%。與甲基和乙基酮衍生物相比，丙基酮衍生物有較高的活性,而且丙基酮衍生物的碳碳鍵活化反應甚至能在50°C 的低溫條件下進。
根據化學計學，環酮的碳碳鍵開環反應顯示RhIII(ttp)OH 是斷開C(CO)-C(α)鍵的中間體。
進一步的反應機研究表明， RhIII(ttp)OH 的羥基是從水中得。RhIII(ttp)X首先進α碳氫鍵活化生成動學產物。經過水解，α碳氫鍵活化產物可以重新形成RhIII(ttp)OH。然後，RhIII(ttp)OH 繼續進碳碳鍵活。
另外，經濟的5, 10, 15, 20-(四甲苯) 鈷卟啉絡合物與丙基酮衍生物反應，在室溫下可選擇性進碳碳鍵活化並得到鈷卟啉酰基化合物，產最高達82%。根據化學計學，CoIII(ttp)OH 被認為是碳碳鍵活化的中間體。CoIII(ttp)OH很有可能是通過鈷卟啉與水的歧化反應生成的。
This thesis focuses on the reactivities and mechanistic studies of the rhodium and cobalt porphyrins (M(por)X) assisted selective carbon(CO)-carbon(α) bond activation (CCA) of unstrained ketones with water.
Unstrained aromatic and aliphatic ketones reacted with 5,10,15,20-tetratolylporphyrinato rhodium(III) complexes, Rh[superscript III](ttp)X (X = Cl and Me), at 200°C to give the corresponding rhodium porphyrin acyls as the CCA products up to 97% yield. Isopropyl ketones exhibit much higher reactivities over methyl and ethyl ketones and the CCA can even occur at a low temperature of 50 °C.
The ring openmg CCA of cyclic ketones suggests the carbon(CO)-carbon(α)bond is cleaved by Rh(ttp )OH according to the reaction stoichiometry.
Further mechanistic investigations suggest that water is the source of hydroxyl group to form Rh[superscript III](ttp)OH. Rh[superscript III](ttp)X first undergoes α-carbon-hydrogen bond activation (α-CHA) to give a kinetic product. Hydrolysis of the α-CHA complex affords Rh[superscript III](ttp)OH for subsequent CCA process.
Alternatively, the economically attractive 5,1 0,15,20-tetratolylporphyrinato cobalt(II) complexes, Co[superscript II](ttp), reacted chemoselectively with isopropyl ketones at the carbon(CO)-carbon(α) bond under room temperature to give high yields of cobalt porphyrin acyls up to 82% yields. Co[superscript III](ttp)OH is identified to be the CCA intermediate as suggested by the reaction stoichiometry. Generation of Co[superscript III](ttp )OH from Co[superscript II](ttp) via the disproportionation with water is proposed.
Detailed summary in vernacular field only.
Detailed summary in vernacular field only.
Detailed summary in vernacular field only.
Detailed summary in vernacular field only.
Detailed summary in vernacular field only.
Fung, Hong Sang.
Thesis (Ph.D.)--Chinese University of Hong Kong, 2012.
Includes bibliographical references.
Electronic reproduction. Hong Kong : Chinese University of Hong Kong, [2012] System requirements: Adobe Acrobat Reader. Available via World Wide Web.
Abstract also in Chinese.
Abstract --- p.i
Acknowledgements --- p.iv
Table of Contents --- p.v
Abbreviations --- p.ix
Structural Abbreviations for Porphyrins --- p.x
Chapter Chapter 1 --- General Introduction --- p.1
Chapter 1.1 --- General Introduction to Carbon-Carbon Bond Cleavage --- p.1
Chapter 1.1.1 --- Organic Examples of Carbon-Carbon Bond Cleavage --- p.1
Chapter 1.1.2 --- Carbon-Carbon Bond Activation with Transition Metal 2Complexes --- p.2
Chapter 1.1.2.1 --- Ring Strain Relief --- p.2
Chapter 1.1.2.2 --- Chelation Assistance --- p.3
Chapter 1.1.2.3 --- Aromatization --- p.3
Chapter 1.1.2.4 --- Carbonyl Functionality --- p.4
Chapter 1.1.2.5 --- β-Alkyl Elimination --- p.4
Chapter 1.1.2.6 --- Formal Alkane Metathesis --- p.5
Chapter 1.2 --- Carbon-Carbon Bond Cleavage of Ketones --- p.6
Chapter 1.2.1 --- Properties of Ketones --- p.6
Chapter 1.2.2 --- Organic Examples of Carbon-Carbon Bond Cleavage of Ketones --- p.7
Chapter 1.2.2.1 --- Haloform Reaction --- p.8
Chapter 1.2.2.2 --- Haller-Bauer Reaction --- p.8
Chapter 1.2.2.3 --- Baeyer-Villiger & Dakin Oxidation --- p.9
Chapter 1.2.2.4 --- Beckmann & Schmidt Rearrangement --- p.10
Chapter 1.2.2.5 --- Favorskii Rearrangement --- p.11
Chapter 1.2.2.6 --- Norrish Type I Reaction --- p.12
Chapter 1.2.2.7 --- Hydrolysis with Water --- p.12
Chapter 1.2.3 --- Carbon(CO)-Carbon(α) Bond Activation of Ketones with Transition Metal Complexes --- p.13
Chapter 1.2.3.1 --- Stoichiometric C(CO)-C(α) Bond Activation of Ketones --- p.18
Chapter 1.2.3.1.1 --- Metal Insertion into Strained Ring --- p.18
Chapter 1.2.3.1.2 --- Decarbonylation --- p.19
Chapter 1.2.3.1.3 --- Chelation Assisted CCA of Unstrained Ketones --- p.19
Chapter 1.2.3.1.4 --- Reaction with Benzyne Complex --- p.20
Chapter 1.2.3.1.5 --- Reaction with Metal Hydroxide --- p.21
Chapter 1.2.3.2 --- Catalytic C(CO)-C(α) Bond Activation of Ketones --- p.22
Chapter 1.2.3.2.1 --- Decarbonylation --- p.22
Chapter 1.2.3.2.2 --- Insertion with Unsaturated Compounds --- p.23
Chapter 1.2.3.2.3 --- Hydrogenolysis --- p.24
Chapter 1.2.3.2.4 --- Ring Fusion --- p.25
Chapter 1.3.3.2.5 --- [4+2+2] Annulation --- p.26
Chapter 1.2.3.2.6 --- Alcoholysis and Aminolysis --- p.27
Chapter 1.2.3.2.7 --- Hydroarylation --- p.28
Chapter 1.2.3.2.8 --- Arylative Ring Expansion with Alkynes --- p.29
Chapter 1.3 --- Water as An Oxidizing Agent --- p.29
Chapter 1.3.1 --- Water-Gas Shift Reaction --- p.30
Chapter 1.3.2 --- Hydration of C-C π-Bond --- p.31
Chapter 1.3.3 --- Cleavage of C≡C Bond --- p.31
Chapter 1.3.4 --- Oxidation of C-H Bond --- p.32
Chapter 1.4 --- Transition Metal Hydroxide Chemistry --- p.33
Chapter 1.4.1 --- Preparation of Group 9 Metal Hydroxides --- p.34
Chapter 1.4.1.2 --- Ligand Substitution --- p.34
Chapter 1.4.1.3 --- Oxidative Addition --- p.34
Chapter 1.4.1.4 --- Hydrolysis --- p.35
Chapter 1.4.2 --- Chemistry of Transition Metal Hydroxide --- p.35
Chapter 1.5 --- Introduction to Porphyrins and Group 9 Metalloporphyrins --- p.37
Chapter 1.5.1 --- Porphyrin Ligand --- p.37
Chapter 1.5.2 --- Metalloporphyrins --- p.38
Chapter 1.5.3 --- Chemistry of Group 9 Metalloporphyrins --- p.39
Chapter 1.5.3.1 --- M[superscript I](por) Chemistry --- p.40
Chapter 1.5.3.2 --- M[superscript II](por) Chemistry --- p.41
Chapter 1.5.3.3 --- M[superscript III](por) Chemistry --- p.44
Chapter 1.5.4 --- Equilibration of MI(por), MI (por) and MIII(por) --- p.46
Chapter 1.5.5 --- Chemistry of Group 9 Metalloporphyrin Hydroxide --- p.47
Chapter 1.5.5.1 --- Metalloether Formation --- p.47
Chapter 1.5.5.2 --- Reductive Dimerization --- p.48
Chapter 1.5.5.3 --- Oxidation --- p.49
Chapter 1.5.5.4 --- Carbon-Hydrogen Bond Activation --- p.50
Chapter 1.5.5.5 --- Carbon-Carbon Bond Activation --- p.51
Chapter 1.6 --- Scope of Thesis --- p.52
Chapter Chapter 2 --- Carbon(CO)-Carbon(α) Bond Activation of Ketones with Rhodium(lII) Porphyrin Complexes --- p.63
Chapter 2.1 --- Introduction --- p.63
Chapter 2.2 --- Objectives of the Work --- p.66
Chapter 2.3 --- Preparation of Starting Materials --- p.66
Chapter 2.3.1 --- Synthesis of Porphyrin --- p.66
Chapter 2.3.2 --- Synthesis of Rhodium(III) Porphyrin Chloride --- p.67
Chapter 2.3.3 --- Synthesis of Rhodium(III) Porphyrin Methyl --- p.67
Chapter 2.3.4 --- Synthesis of Rh[superscript III](ttp)H --- p.68
Chapter 2.3.5 --- Synthesis of Rh[superscript II]₂(ttp)₂ --- p.68
Chapter 2.3.6 --- Synthesis of Rh[superscript I](ttp)-Na⁺ --- p.68
Chapter 2.4 --- Optimization of Reaction Conditions with Acetophenone --- p.68
Chapter 2.4.1 --- Reaction with Rh[superscript III](ttp )OTf, Rh[superscript III](ttp)Cl and Rh[superscript III](ttp)Me --- p.68
Chapter 2.4.2 --- Temperature Effect --- p.70
Chapter 2.4.3 --- Porphyrin Ligand Effect --- p.70
Chapter 2.5 --- Substrate Scope of the CCAReaction --- p.71
Chapter 2.5.1 --- CCA of Acetophenones --- p.71
Chapter 2.5.2 --- CCA of Aromatic and Aliphatic Ketones --- p.72
Chapter 2.6 --- Low Temperature CCA with Isopropyl Ketones --- p.76
Chapter 2.7 --- Oxidation of the C(CO)-C(α) Bond --- p.77
Chapter 2.8 --- Water as a Source of Oxidant --- p.80
Chapter 2.9 --- Regioselectivity of CCA --- p.81
Chapter 2.1 --- 0 X-ray Structure Determination --- p.83
Chapter 2.11 --- Mechanistic Studies --- p.92
Chapter 2.11.1 --- Proposed Mechanism --- p.92
Chapter 2.11.2 --- Aldol Condensation Catalyzed by Rh(ttp)X (X = Me or Cl) --- p.93
Chapter 2.11.3 --- Carbon-Hydrogen Bond Activation with Rh(ttp)X (X = Me or Cl) --- p.94
Chapter 2.11.4 --- Hydrolysis of the α-CHA Product 100 --- p.100
Chapter 2.11.5 --- Carbon(CO)-Carbon(α) Bond Oxidation with Rh(ttp)OH --- p.102
Chapter 2.11.6 --- Dehydrogenation of Alcohol --- p.108
Chapter 2.11.7 --- Thermodynamic Consideration --- p.109
Chapter 2.12 --- Conclusion --- p.110
Chapter Chapter 3 --- Carbon(CO)-Carbon(α) Bond Activation of Ketones with Cobalt(II)Porphyrin Complexes --- p.114
Chapter 3.1 --- Introduction --- p.114
Chapter 3.2 --- Objectives of the Work --- p.115
Chapter 3.3 --- Preparation of Starting Materials --- p.115
Chapter 3.3.1 --- Synthesis of H₂(tp-clPP) --- p.115
Chapter 3.3.2 --- Synthesis of Co[superscript II] (por) --- p.116
Chapter 3.4 --- Strategies of C(CO)-C(α) Bond Activation with Cobalt(II) Porphyrins --- p.116
Chapter 3.5 --- Optimization of Reaction Conditions with Diisopropyl Ketone --- p.118
Chapter 3.5.1 --- Solvent Effect --- p.118
Chapter 3.5.2 --- Water Effect --- p.119
Chapter 3.5.3 --- PPh3 Effect --- p.120
Chapter 3.5.4 --- Porphyrin Ligand Effect --- p.121
Chapter 3.5.5 --- Temperature Effect --- p.122
Chapter 3.6 --- CCA of Isopropyl Ketones --- p.123
Chapter 3.7 --- X-ray Structure Determination --- p.126
Chapter 3.8 --- Mechanistic Studies --- p.131
Chapter 3.8.1 --- Proposed Mechanism --- p.131
Chapter 3.8.2 --- Disproportionation of Co[superscript II](ttp) with Water --- p.132
Chapter 3.8.3 --- Dehydrogenation of Co[superscript III](ttp)H --- p.132
Chapter 3.8.4 --- C(CO)-C(α) Bond Activation --- p.134
Chapter 3.8.5 --- Dehydrogenation of the Alcohol --- p.134
Chapter 3.8.6 --- Overall Enthalpy Change --- p.134
Chapter 3.9 --- Stoichiometric Functionalization --- p.135
Chapter 3.10 --- Conclusion --- p.138
Chapter Chapter 4 --- Comparison on Carbon-Carbon Bond Activation by Cobalt, Rhodium and Iridium Porphyrin --- p.142
Chapter 4.1 --- Introduction --- p.142
Chapter 4.2 --- Reactivities of Metalloporphyrins --- p.143
Chapter 4.3 --- Thermodynamic of CCA --- p.144
Chapter 4.4 --- Rate of CCA --- p.147
Chapter 4.5 --- Scope and Reactivities of Ketones --- p.147
Chapter 4.6 --- Regioselectivities --- p.149
Chapter 4.7 --- Chemoselectivity --- p.150
Chapter 4.8 --- Conclusion --- p.152
Chapter Chapter 5 --- Experimental Section --- p.153
Appendices --- p.181