Mechanistic investigation of catalytic organometallic reactions using ESI MS

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dc.contributor.author Luo, Jingwei
dc.date.accessioned 2014-12-16T16:28:03Z
dc.date.available 2014-12-16T16:28:03Z
dc.date.copyright 2014 en_US
dc.date.issued 2014-12-16
dc.identifier.uri http://hdl.handle.net/1828/5767
dc.description.abstract Electrospray ionization mass spectrometry (ESI-MS) has been applied to the real time study of air-sensitive homogenous organometallic catalytic reactions due to its soft ionization properties. Therefore, fragile molecules and complexes in these reactions were characterized. The kinetic studies of these reactions have also been done by following the relative abundance of different species including starting material(s), products, by-product(s) as well as intermediates. Based on the results, reaction pathways and mechanisms were proposed and numerical models were built to accurately mimic the reactions under specific condition. In order to make the reactions detectable by ESI-MS, many charged ESI-MS friendly substrates were synthesized as tracking tags, including 1-allyl-1-(prop-2-yn-1-yl)piperidin-1-ium hexafluorophosphate(V), 1-allyl-1-(prop-2-yn-1-yl)pyrrolidin-1-ium hexafluorophosphate(V), (4-ethynylbenzyl)triphenylphosphonium hexafluorophosphate(V), hex-5-yn-1-yltriphenylphosphonium hexafluorophosphate(V) etc. The method for continuously monitoring water- and oxygen-sensitive reactions in real time named pressurized sample infusion (PSI) was developed, optimized and applied throughout all the projects in the thesis. These techniques were applied to detailed studies of the intramolecular Pauson-Khand reaction (PKR) with Co2CO8 under different temperatures. The kinetic study results gave the entropy and enthalpy of the reaction and evidence suggested that the ligand dissociation step was the rate-determining step of the reaction. Hydrogenation of alkynes with Wilkinson’s catalyst and Weller’s catalyst were also studied using PSI. The behaviour of starting materials and products were tracked, then various reactions were carried out by using different temperatures and concentrations. Furthermore, competition reaction and kinetic isotope effect study, mechanisms were proposed based on experimental results, numerical models were built, and rate constants for each step were estimated. Different Si-H activation reactions were studied including hydrolysis of silanes, hydrosilation, dehydrocoupling of silanes, alcoholysis of silane and silane redistribution by using (3-(methylsilyl)propyl)triphenylphosphonium hexafluorophosphate(V). A variety of collaborative projects were also carried out including hydroacylation, fast-activating Pd catalyst precursor, catalyst analysis for Cu-mediated fluorination, CdSe - NiDHLA analysis, Ru catalyzed propargylic amination reaction, Zn catalyzed lactide polymerization, and Fe4S4 clusters. en_US
dc.language English eng
dc.language.iso en en_US
dc.rights.uri http://creativecommons.org/licenses/by-nc-nd/2.5/ca/ *
dc.subject ESI MS en_US
dc.subject Mechanistic en_US
dc.subject organometallic en_US
dc.subject catalysis en_US
dc.title Mechanistic investigation of catalytic organometallic reactions using ESI MS en_US
dc.type Thesis en_US
dc.contributor.supervisor McIndoe, J. Scott
dc.degree.department Department of Chemistry en_US
dc.degree.level Doctor of Philosophy Ph.D. en_US
dc.rights.temp Available to the World Wide Web en_US
dc.identifier.bibliographicCitation M. A. Henderson, J. Luo, A. Oliver and J. S. McIndoe, Organometallics, 2011 en_US
dc.identifier.bibliographicCitation K. L. Vikse, Z. Ahmadi, J. Luo, N. van der Wal, K. Daze, N. Taylor and J. S. McIndoe, Int. J. Mass Spectrom., 2012, 323–324, 8-13. en_US
dc.identifier.bibliographicCitation J. Luo, A. G. Oliver and J. Scott McIndoe, Dalton Trans., 2013, 42, 11312-11318. en_US
dc.description.scholarlevel Graduate en_US

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