Chemistry of metal complexes in the gas phase

Gholami, Ameneh (2013) Chemistry of metal complexes in the gas phase. Masters thesis, Memorial University of Newfoundland.

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Gas phase chemistry of ions provides important insight into the reactivity, thermochemistry, reaction mechanisms, and structures of ions without the added complexity of solvent. Fourier Transform Ion Cyclotron Resonance (FT-ICR) mass spectrometry is the most commonly used and ideally suited technique to study chemistry of ions in the gas phase. The ICR cell is like a small laboratory with controllable conditions, where ions are trapped and undergo reactions, therefore elementary steps of reactions can be easily tracked. Structural studies employing activation/fragmentation techniques such as infrared multiple photon dissociation (IRMPD) or sustained off resonance irradiation collisionally induced dissociation (SORI-CID) can be easily conducted using an FTICR instrument. -- This thesis presents study of transition metal complexes reactions with neutral molecules in the gas phase. The first kinetic experiments were conducted for the association reactions of unsaturated ruthenium complexes [Ru(bipy)X]²⁺ (X bipyridine, 2-(pyridin-4-yl)-1, 3-benzothiazole, or 5-aminophenathroline) with CO and O₂ to explore mechanism of the ion-molecule reactions in the low pressure environment of the ICR cell. The association adduct complex [Ru(bipy)₂CO]²⁺ was then used to activate C-H or C-C bonds of various alkanes. Computational chemistry was also employed to further investigate the mechanism of the dehydrogenation and demethanation reactions between chemically activated [Ru(bipy)₂CO]²⁺ and alkane molecules. -- Finally, structures and fragmentation pathways of Zn²⁺ complexes with proline were studied. IRMPD spectroscopy in conjunction with computational chemistry was used to explore the structures of the deprotonated zinc-proline complex, [Zn(Pro-H)]⁺, and the singly hydrated complex [Zn(Pro-H)(H₂O)]⁺. Furthermore, fragmentation reactions of deprotonated zinc-amino acid dimer complexes [Zn(A-H)(A)]⁺ (A = proline, sarcosine, alanine, and glycine) were studied using IRMPD and SORI-CID. The different fragmentation channels observed for secondary amine complexes, proline and sarcosine, and primary amine complexes, alanine and glycine, were interpreted by computational chemistry results.

Item Type: Thesis (Masters)
Item ID: 10543
Additional Information: Includes bibliographical references.
Department(s): Science, Faculty of > Chemistry
Date: 2013
Date Type: Submission
Library of Congress Subject Heading: Metal ions--Spectra; Ion-molecule collisions; Ionized gases; Ion cyclotron resonance spectrometry.

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