A MATRIX ISOLATION SPECTROSCOPIC INVESTIGATION INTO THE REACTION PRODUCTS OF VANADIUM METAL ATOMS WITH PROPENE

• Main Author: Walker, Stephen
• Other Authors: Queen's University (Kingston, Ont.). Theses (Queen's University (Kingston, Ont.))
• Format: Others
• Language: en; en
• Published: 2009
• Subjects: Matrix isolation; Infrared; Propene; Vanadium; C-H insertion
• Online Access: http://hdl.handle.net/1974/2597

The products of vanadium metal atom reactions with propene and some propene isotopomers (propene-d6 and propene-3,3,3-d3) are investigated using FT-IR matrix isolation. The major product from the condensation of V atoms with propene at elevated mole ratios is found to be propane (C3H8), the production of which is seen to increase as concentration of propene increases. Additionally a matrix isolated product formed after metal atom insertion into the C-H bond of propene at low propene mole ratios is isolated and identified. The location of the insertion site is identified as one of the methyl hydrogen carbon bonds. The structure of the product is identified as an allyl vanadium hydride complex, through a FT-IR matrix isolation study of propene isotopomers. It is also shown that this primary product acts as an intermediate in the formation of propane. A full mechanism for the proposed formation of propane from sacrificial hydrogenation is proposed and compared with the reported mechanism for the similar reaction involving ethene. The mechanistic identification of the hydrogenation of propene is shown as a generalization of the previous reaction involving ethene. Photochemistry of reactants and intermediates trapped in the matrix are investigated. Irradiation of matrices with several different UV-visible wavelength ranges indicate that no further chemistry occurs after formation of the matrix and further irradiation has no effect on intermediates or reactants. Additionally the reactivity of water with vanadium and propene under low propene concentration conditions is also studied. Results from this study show that under all conditions studied no incorporation of water into the propene molecule is found. === Thesis (Master, Chemistry) -- Queen's University, 2009-08-10 11:15:55.312