- Library Home /
- Search Collections /
- Open Collections /
- Browse Collections /
- UBC Theses and Dissertations /
- Kinetics and mechanism of hydrogenolysis of a ruthenium(II)...
Open Collections
UBC Theses and Dissertations
UBC Theses and Dissertations
Kinetics and mechanism of hydrogenolysis of a ruthenium(II) acyl complex Joshi, Ajey Madhav
Abstract
This thesis describes the results of kinetic investigations into the hydrogenolysis of the ruthenium-acyl complex dicarbonylchloro-(norbornenoyDbis(triphenylphosphine)ruthenium(II ),RuCl(CO⋅C₇H₉) (CO) ₂-(PPh₃)₂. 2. N,N-Dimethylacetamide (DMA) and toluene solutions of 2 react with one mole equivalent of H₂ to give HRuCl(CO)₂(PPh₃)₂, 3, and the unsaturated aldehyde product C₇H₉CHO, 4. The subsequent, relatively slow hydrogenation of 4 by a further mole of H₂ to give the saturated aldehyde C₇H₁₁-CHO, 5, was found to be catalyzed by 3. A detailed kinetic study on the hydrogenolysis of 2 in DMA solvent revealed a first-order rate dependence on [Ru][sub Total] an inverse dependence on added [PPh₃], and a first- to zero-order dependence on H₂pressure. The following mechanism is proposed to account for these observations: [See Thesis for Diagram] Values of k₁ and k₋₁/k₂ have been evaluated at 65°C (k₁ = 4.6±0.5x10⁻⁵ s⁻¹ k₋₁/k₂ = 1.7±0.2) and the activation enthalpy and entropy for the k₁ step determined (ΔH[sup ‡] = 69±7 kJmole⁻¹, Δs‡ = -126+13 JK⁻¹ mole⁻¹). New, and as yet incompletely characterized, ruthenium complexes of stoichiometry "RuCl(C₆H₉)(PPh₃)₂”, 6, HRuCl(C₆H₈)(C₆H₉)(PPh₃)₂-benzene solvate", 7, and RuCl₂(C₆H₈)(PPh₃)₂, 8, have been synthesized by the reactions of 1,4-cyclohexadiene (C₆H₈) with HRuCl(PPh₃)₃⋅C₆H₆ (complexes 6 and 7), and RuCl₂ (PPh₃)₃ (complex 8), respectively. Reactions of 6, 7, and 8 in DMA with H₂ and with CO were investigated, and the organic and inorganic products identified: [See Thesis for Diagram]
Item Metadata
Title |
Kinetics and mechanism of hydrogenolysis of a ruthenium(II) acyl complex
|
Creator | |
Publisher |
University of British Columbia
|
Date Issued |
1986
|
Description |
This thesis describes the results of kinetic investigations into the hydrogenolysis of the ruthenium-acyl complex dicarbonylchloro-(norbornenoyDbis(triphenylphosphine)ruthenium(II ),RuCl(CO⋅C₇H₉) (CO) ₂-(PPh₃)₂. 2. N,N-Dimethylacetamide (DMA) and toluene solutions of 2 react with one mole equivalent of H₂ to give HRuCl(CO)₂(PPh₃)₂, 3, and the unsaturated aldehyde product C₇H₉CHO, 4. The subsequent, relatively slow hydrogenation of 4 by a further mole of H₂ to give the saturated aldehyde C₇H₁₁-CHO, 5, was found to be catalyzed by 3.
A detailed kinetic study on the hydrogenolysis of 2 in DMA solvent revealed a first-order rate dependence on [Ru][sub Total] an inverse dependence on added [PPh₃], and a first- to zero-order dependence on H₂pressure. The following mechanism is proposed to account for these observations: [See Thesis for Diagram]
Values of k₁ and k₋₁/k₂ have been evaluated at 65°C (k₁ = 4.6±0.5x10⁻⁵ s⁻¹ k₋₁/k₂ = 1.7±0.2) and the activation enthalpy and entropy for the k₁ step determined (ΔH[sup ‡] = 69±7 kJmole⁻¹, Δs‡ = -126+13 JK⁻¹ mole⁻¹).
New, and as yet incompletely characterized, ruthenium complexes of stoichiometry "RuCl(C₆H₉)(PPh₃)₂”, 6, HRuCl(C₆H₈)(C₆H₉)(PPh₃)₂-benzene solvate", 7, and RuCl₂(C₆H₈)(PPh₃)₂, 8, have been synthesized by the reactions of 1,4-cyclohexadiene (C₆H₈) with HRuCl(PPh₃)₃⋅C₆H₆ (complexes 6 and 7), and RuCl₂ (PPh₃)₃ (complex 8), respectively. Reactions of 6, 7, and 8 in DMA with H₂ and with CO were investigated, and the organic and inorganic products identified: [See Thesis for Diagram]
|
Genre | |
Type | |
Language |
eng
|
Date Available |
2010-06-20
|
Provider |
Vancouver : University of British Columbia Library
|
Rights |
For non-commercial purposes only, such as research, private study and education. Additional conditions apply, see Terms of Use https://open.library.ubc.ca/terms_of_use.
|
DOI |
10.14288/1.0059337
|
URI | |
Degree | |
Program | |
Affiliation | |
Degree Grantor |
University of British Columbia
|
Campus | |
Scholarly Level |
Graduate
|
Aggregated Source Repository |
DSpace
|
Item Media
Item Citations and Data
Rights
For non-commercial purposes only, such as research, private study and education. Additional conditions apply, see Terms of Use https://open.library.ubc.ca/terms_of_use.