Thesis (M. Sc.)--York University, 2002. Graduate Programme in Chemistry. / Typescript. Includes bibliographical references (leaves 83-87). Also available on the Internet. MODE OF ACCESS via web browser by entering the following URL: http://wwwlib.umi.com/cr/yorku/fullcit?pMQ71628.

241 leaves : ill., tables ; 30 cm. / Title page, contents and abstract only. The complete thesis in print form is available from the University Library. / Thesis (Ph.D.)--University of Adelaide, Dept. of Physical and Inorganic Chemistry, 1978

Thesis (Ph.D.) -- University of Adelaide, Department of Physical and Inorganic Chemistry, 1978.

The previously known complexes, RU₂H₄Cl₂(PR₃)₄, have now been correctly reformulated as the η²-H₂ species (η²-H₂)(PR₃)₂Ru(μ-Cl)₂(μ-H)RuH(PR₃)₂ (R = Ph, p-tol), 1a and 1b, and it is confirmed that in solution they are dimeric and undergo no ligand dissociation. Also, a new analogue of complexes of type 1 is reported: the complex (η²-H₂)(isoPFA)Ru(μ-Cl)₂(μ-H)RuH(PPh₃)₂,4, is formed from the reaction of RuCl₂(PPh₃)(isoPFA), 3b, with H₂ in methanol/benzene, and a crystal structure of 4 shows the η²-H₂ ligand; isoPFA and PPFA (see below) are ferrocene based, chelating P-N ligands, with the structures: [Chemical compound diagram omitted] R = Pri and Ph for isoPFA and PPFA, respectively. Complexes 1a, 1b and 4 all react with 1-hexene to give hexane; the main ruthenium phosphine product in the case of 1 is the corresponding RuHCl(PR₃)₃ complex, while 4 reacts to give a complex mixture of ruthenium phosphine complexes, including 3b. The amount of hexane formed from the reaction of 4 with hexene is quantified as 2 mol/mol 4. The hydrogenation of 1-hexene catalyzed by 1a is re-interpreted as occurring via the mechanism: (η²-H₂)(PPh₃)₂Ru(μ-Cl)₂(μ-H)RuH(PPh₃)₂ + hexene K₁→(PPh₃)₂Ru(μ-Cl)₂(μ-H)RuH(PPh₃)₂ + hexane (1) (PPh₃)₂Ru(μ-Cl)₂(μ-H)RuH(PPh₃)₂ + H₂ K₂⇆(η²-H₂)(PPh₃)₂Ru(μ-Cl)₂(μ-H)RuH(PPh₃)₂ (2) Reactions of RuCl₂(PPh₃)(PPFA), 3a, and RuCl₂(PPh₃)(isoPFA), 3b, with H₂ have been further studied, in connection with earlier mechanistic studies on hydrogenation of organic substrates catalyzed by complex 3a. The complex 3a reacts with 2-8 atm H₂ in n-butanol to give ruthenium phosphine products including 1a. The complex 3b reacts with H₂ in methanol/benzene to give 4, as mentioned above, as well as a number of unidentified hydrides; in DMA, the reaction of 3b with H₂ gives 1a, 4, RuHCl(PPh₃)(isoPFA) (7), RuHCl(PPh₃)₃ and other unidentified ruthenium phosphine complexes. The product H₂NMe₂+Cl⁻ was also isolated from the methanol/benzene reaction mixture, and this product provides evidence that the amine functionality of the P-N ligands is involved in the promotion of the heterolytic cleavage of dihydrogen to give a proton and a hydride (H₂→ H⁺ + H⁻). Kinetic studies on the hydrogenation of 1-hexene catalyzed by 3a, and by 3b in the present work, are now interpreted according to the mechanism [Chemical compound diagram omitted] Reactions involving 3b and methanol have also been studied, and 3b is also active for the transfer hydrogenation (from methanol) of ketones and activated olefins. The reaction of 3b with methanol in the absence of base is proposed to occur with the stoichiometry: RuCl₂(PPh₃)(isoPFA) + 2MeOH→ H₂NMe₂⁺Cl⁻ + H₂ + 3b RuHCl(CO)(PPh₃)(isoPOF), 5 (5) where the ligand isoPOF is formed from isoPFA by replacement of the NMe₂ group on isoPFA by a methoxo group; reaction 6 could occur via the following steps: RuCl₂(PPh₃)(isoPFA) + MeOH→ RuHCl(CO)(PPh₃)(isoPFA), 6 3b + H₂ + HCl (6) RuHCl(CO)(PPh₃)(isoPFA) + MeOH→ RuHCl(CO)(PPh₃)(isoPOF), 5 + HNMe₂ (7) HCl + HNMe₂ H₂NMe₂⁺Cl⁻ (8) A mechanism for reaction 7 is presented and invokes reversible attack by MeOH with replacement of Cl⁻, followed by reversible deprotonation of coordinated MeOH to give successively methoxo, formaldehyde and formyl intermediates, and finally the hydrido-carbonyl, 6. The reaction of 3b with methanol in the presence of KOH is proposed to occur according to the stoichiometry: RuCl₂(PPh₃)(isoPFA) + KOH + CH₃OH→ RuHCl(CO)(PPh₃)(isoPFA) + KCI + H₂ + H₂O (9) and two pathways have been identified, one base-independent, identical to that proposed for reaction 7, and one showing a second-order dependence on KOH. The latter pathway invokes initial reversible attack on RuCl₂(PPh₃)(isoPFA), 3b, by MeO⁻, replacing Cl⁻ to give RuCl(OMe)(PPh₃)(isoPFA), and subsequent reversible replacement of PPh₃ by OH⁻, followed by concerted loss of OH⁻ and hydride transfer from coordinated OMe⁻ to give a hydrido-formaldehyde complex RuHCl(η²-CH₂O)(isoPFA). A subsequently formed formyl intermediate reacts via intramolecular hydride transfer from the formyl to the metal, H₂ loss, and phosphine coordination to give the hydrido-carbonyl 6. / Science, Faculty of / Chemistry, Department of / Graduate

Thesis (Ph.D.) - University of St Andrews, October 2008.

published_or_final_version / Chemistry / Doctoral / Doctor of Philosophy

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

"December 2003" / Bibliography: leaves 229-240. / x, 240 leaves : ill. (some col.) ; 30 cm. / Title page, contents and abstract only. The complete thesis in print form is available from the University Library. / Thesis (Ph.D.)--University of Adelaide, School of Chemistry and Physics, Discipline of Chemistry, 2004

Thesis (Ph. D.)--University of Hong Kong, 2001. / Includes bibliographical references (leaves 197-212).

published_or_final_version / Chemistry / Doctoral / Doctor of Philosophy