Understanding Chemical Reactions In Novel Materials: From Metal Organic Frameworks to Oxyallyl Cations

Abstract

The work of this dissertation investigates the chemical processes of novel materials through quantum mechanical calculations and molecular dynamics simulations. The first section of this work focuses on probing copper based metal organic frameworks (MOFs) for their ability to catalytically release nitric oxide from s-nitrosothiol (RSNO) precursors in a slow, controlled and sustained manner and compares these findings to a free copper ion/ethanol solution. Through the use of electronic structure calculations and molecular dynamics simulations, studies are carried out to better understand how the barriers of RSNOs approach to the catalytic copper center changes with modifications to the R-group (of the RSNO) and the organic linkers of the MOF. In addition to the above-mentioned work, electronic structure calculations were employed to investigate the origins of regioselectivity for silylenol ether products generated from disubstituted ketones through a unimolecular nucleophilic substitution (SN1) reaction mechanism. Synthesis of these materials is highly desired as a result of current chemistries lacking sufficient methods to steer the synthesis of natural product inspired molecules without the use of steric and electronic bias.