Anaerobic electrospray ionization mass spectrometry of methylalumoxane and zirconium complexes
| dc.contributor.author | Joshi, Anuj | |
| dc.contributor.supervisor | McIndoe, J. Scott | |
| dc.date.accessioned | 2020-12-23T06:28:33Z | |
| dc.date.available | 2020-12-23T06:28:33Z | |
| dc.date.copyright | 2020 | en_US |
| dc.date.issued | 2020-12-22 | |
| dc.degree.department | Department of Chemistry | |
| dc.degree.level | Doctor of Philosophy Ph.D. | en_US |
| dc.description.abstract | In this thesis, the reactivity and synthesis of methylalumoxane (MAO) via electrospray ionization mass spectrometry (ESI-MS) was investigated. The olefin polymerization catalyst [Cp2Zr(μ-Me)2AlMe2]+ [B(C6F5)4]− was also used to evaluate the efficacy of a nitrogen generator as a source for desolvation gas for ESI-MS analysis. The same catalyst was then used to study catalyst deactivation after 1-hexene addition. MAO ionizes very selectively in the presence of octamethyltrisiloxane (OMTS) to generate [Me2Al·OMTS]+ [(MeAlO)16(Me3Al)6Me]−. The advantage of this transformation was used to examine the reactivity and synthesis of MAO. The reactivity of this ion pair with other trialkyl aluminum (R3Al) components was studied both offline and in real-time. The exchanges are fast and reversible, and the methyl groups on the cation are also observed to exchange with the added R3Al species. MAO is also famously intractable to structural elucidation, consisting as it does of a complex mixture of oligomers generated from hydrolysis of pyrophoric trimethylaluminum (TMA). Synthesis of MAO was probed in real-time by ESI-MS, and the principal activated product of the benchtop synthesis was found to be the same as that observed in industrial samples, namely [(MeAlO)16(Me3Al)6Me]–. Computationally, a new sheet structure for this ion was proposed. The increasing competitiveness of nitrogen generators, which provide gas purity levels that vary inversely with flow rate, prompted an investigation of the effect of gas-phase oxygen on the speciation of ions by ESI-MS. The most reactive species studied, the reduced titanium complex [Cp2Ti(NCMe)2]+[ZnCl3]− and the olefin polymerization pre-catalyst [Cp2Zr(μ-Me)2AlMe2]+[B(C6F5)4]−, only exhibited detectable oxidation when they were rendered coordinatively unsaturated through in-source fragmentation. The catalyst [Cp2Zr(μ-Me)2AlMe2]+[B(C6F5)4]− was further studied by ESI-MS to understand better the complexities of catalyst deactivation in the polymerization of 1-hexene. I also contributed to other projects, namely the interaction of neutral donors with MAO, saturation problems in ESI-MS, and ligand substitution reaction in ruthenium complexes, and my work on all these projects are summarized in this thesis. | en_US |
| dc.description.scholarlevel | Graduate | en_US |
| dc.identifier.uri | http://hdl.handle.net/1828/12491 | |
| dc.language | English | eng |
| dc.language.iso | en | en_US |
| dc.rights | Available to the World Wide Web | en_US |
| dc.subject | Olefin polymerization | en_US |
| dc.subject | metallocene catalyst | en_US |
| dc.subject | electrospray ionization mass spectrometry | en_US |
| dc.subject | methylalumoxane | en_US |
| dc.subject | activators | en_US |
| dc.subject | cocatalyst | en_US |
| dc.subject | aluminum alkyls | en_US |
| dc.subject | nitrogen generator | en_US |
| dc.title | Anaerobic electrospray ionization mass spectrometry of methylalumoxane and zirconium complexes | en_US |
| dc.type | Thesis | en_US |