Studies of the mechanisms and energetics of a variety ion-molecule reactions involving organometallic and organic ions, have been performed using Fourier transform ion cyclotron resonance mass spectrometry (FTMS). The bond activation processes of V⁺, VO⁺, VOH⁺, and VOCH₃⁺ with water and methanol were investigated in detail. All ions are observed to preferentially activate the C-O bond in methanol, however C-H and O-H bond cleavage are also observed. The addition of the oxo, hydroxo, and methoxo ligands is found to significantly effect the intrinsic reactivity of the ions, relative to V⁺. The reactions of V(CO)₅⁻ with a wide variety of molecules have revealed mechanistic details of the oxidative addition and ligand switching reactions. Steric effects are proposed to account for the selective reactivity of V(CO)₅⁻ with alcohols and amines. Studies of ligand substitution reactions support an electron transfer initiated mechanism, implying that V(CO)₅⁻ has a triplet ground state and a trigonal bipyramidal structure. The chlorine atom transfer reactions of V(CO)₅⁻ with chloromethanes display a correlation with C-CI bond strength, suggesting the mechanism is initiated by oxidative addition of the C-C1 bond or involves a direct chlorine atom transfer. The decomposition of metallocarboxylate anions ([M(CO)ₓ₋₁CO₂]⁻) was studied in an effort to understand the production of CO₂ by metal carbonyl compounds, proposed as intermediates in the Water-Gas shift reaction. The nascent [M(CO)ₓ₋₁C0₂]⁻*, formed by nucleophilic addition of 0⁻ to M(CO)ₓ (M=Pe, Cr, V), is observed to undergo exclusive loss of CO₂ without subsequent decomposition of the product metal carbonyl anion (M(CO)ₓ₋₁⁻) The reaction of P AHs with O⁻ and O₂⁻ were studied, to investigate the potential of isomer differentiation by chemical ionization. These reactions are characterized by a number of reactive pathways, demonstrating the ability to distinguish isomers which cannot be differentiated by other ionization techniques. Kinetic energy release measurements of the S(N)2 reactions of F⁻ with CH3CI, C₆H₅CI, and CH₃COCl have been made using KEICR. The F⁻/CH₃Cl reaction results in a non-statistical energy disposal. The reaction is proposed to proceed by a direct mechanism.
| Identifer | oai:union.ndltd.org:arizona.edu/oai:arizona.openrepository.com:10150/186137 |
| Date | January 1993 |
| Creators | Van Orden, Steven Lee. |
| Contributors | Buckner, Steven W., Burke, Michael F., Denton, M. Bonner, Miller, Walter B., Smith, Mark A. |
| Publisher | The University of Arizona. |
| Source Sets | University of Arizona |
| Language | English |
| Detected Language | English |
| Type | text, Dissertation-Reproduction (electronic) |
| Rights | Copyright © is held by the author. Digital access to this material is made possible by the University Libraries, University of Arizona. Further transmission, reproduction or presentation (such as public display or performance) of protected items is prohibited except with permission of the author. |
Page generated in 0.0019 seconds