Applications of Fourier transform ion cyclotron resonance mass spectrometry to characterizing transition metal-ligand systems
Abstract
The goal of this thesis is to extend current knowledge on the gas-phase chemistry of metal-ligand ion systems, specifically M(benzyne)$\sp+$, Fe(phenyl)$\sp+$, and M(methyl)$\sp+$. The gas-phase chemistry of M(benzyne)$\sp+$ (M = Fe, Co, and Rh), was studied with small hydrocarbons and small alkyl halides, CH$\sb3$F and $\rm C\sb{n}H\sb{2n+1}X$ (n = $1-4$; X = Cl, Br, I). A photodissociation study of Co(benzyne)$\sp+$ yielded D$\sp\circ$(Co$\sp+$- benzyne) = 78 $\pm$ 10 kcal/mol. The gas-phase chemistry of Fe(phenyl)$\sp+$ with small alkyl halides was studied. D$\sp\circ$ (Fe$\sp+$-phenyl) = 68 $\pm$ 10 kcal/mol was also determined by photodissociation studies. The reactivity of MCH$\sb3\sp+$ (M = Fe and Co) towards CH$\sb3$X (X = F, Cl, Br, and I) and $\rm C\sb2H\sb5Cl$ was studied. In general, reaction mechanisms are postulated based on the product ion structures which are determined by ion-molecule reactions, photodissociation and collision-induced dissociation. Generally, the reactions are observed to proceed by an initial C-X, C-H, or C-C insertion or by a simple condensation. There are few secondary reactions, and they generally involve halogen abstraction and dehydrohalogenation. Finally, the thermochemical implications of these results are discussed.
Degree
Ph.D.
Advisors
Freiser, Purdue University.
Subject Area
Analytical chemistry
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