published_or_final_version / Chemistry / Doctoral / Doctor of Philosophy

published_or_final_version / abstract / toc / Chemistry / Doctoral / Doctor of Philosophy

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