Master of Science
Ragogna, P. J.
The field of low-coordinate main group chemistry has seen huge development in the last 30 years, with novel compounds that demonstrate unique structures and reactivity. Isolation of these species has relied on thoughtfully designed substituents normally containing substructure steric bulk. The area of phosphinidene chalcogenide isolation and transfer remains poorly understood by comparison. In this context, the major focus of thesis was on the development of a room-temperature method for the transfer of RP=S moieties with and without sterically demanding substituents. The preparation and complete characterization of new asymmetric phosphines with m-terphenyl ligands was also reported. In Chapter 2, the characterization of secondary and tertiary phosphines which have the general formula TerPhPR1R2 (TerPh = 2,6-Mes2C6H3, Mes = 2,4,6-(CH3)3C6H2). In Chapter 3, the utility of the condensation method developed by the Ragogna group for the generation of RP=S in situ for compounds with, and without, sterically bulk groups was demonstrated and included the characterization of a number of [1+2], [2+2], [1+4], and [2+4] P,S-heterocycles. The stoichiometric generation and subsequent transfer of RP=S without bulky ligands or norbornadiene scaffolds was unprecedented in literature and two different mechanistic pathways were hypothesized.
Pritchard, Taylor E., "Exploring the Chemistry of Asymmetric Phosphines & Phosphinidene Sulfides" (2018). Electronic Thesis and Dissertation Repository. 5664.