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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Abstract

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.

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