| Electrospray ionization mass spectrometry (ESI-MS) is a powerful tool for characterizing organometallic catalytic reactions. It does however, have some problems, and this thesis presents three of them along with solutions that have been developed for overcoming these challenges.;Gas phase reactivity has typically been done with highly specialized and sophisticated equipment. However, concurrent with instrument sophistication is cost, leading to decreased access to gas phase reactivity for practicing synthetic chemists seeking only to scan the fundamental reactivity of a given molecule or complex across a range of substrates. This thesis presents a cost effective solution to accessing gas phase chemistry by ESI-MS employing common equipment found in any synthetic laboratory and a case study with the anionic ruthenium cluster [H3Ru4(CO)12]-.;The second development of this thesis involved the synthesis and design of a range of charged alkynes which were used to study the Pauson-Khand reaction. Applying the techniques of gas-phase reactivity, some elusive intermediates were observed in the catalytic cycle.;Polar solvents such as water, acetonitrile, methanol, ethanol, and acetone are most common for ESI-MS, with non-polar solvents such as toluene and hexane being totally inert in the ESI process. Highly sensitive organometallic compounds generally decompose rapidly in polar solvents, hindering the study of these systems by ESI-MS. A discovery presented in this thesis was that addition of lipophilic ionic liquids to hexane or toluene facilitated the required electrochemistry in the ionization process. This allows characterization of highly sensitive organometallic catalysts in solvents such as hexane and toluene that were previously unsuited to study by ESI-MS.;Methylaluminoxane (MAO) is an important cocatalyst in homogeneous Ziegler-Natta polymerization. Despite its importance however, very little structural information is known. This thesis presents the first known ESI-MS study of both MAO and hydrolyzed triisobutylaluminum (TiBA). The presence of several known structural features are apparent in detailed MS/MS experiments, confirming the validity of these results, and for the first time molecular masses of this oligomeric mixture are obtained. Furthermore, results from the hydrolysis of TiBA give insight into a structure that may potentially be an active cocatalyst in the activation process. |
