New aspects of phosphirane chemistry
Date of Issue2014
School of Physical and Mathematical Sciences
This thesis provides a detailed account of author's exploration on new aspects of phosphirane chemistry. Chapter one briefly reviews the theoretical and experimental works on phosphiranes that have been published until the middle of 2014. Chapter two describes the investigation on the influence of additional strain on phosphiranes. The subjects of the investigation are norbornane-annulated 1-methylphosphirane complexes. The stereochemistry of these complexes has further strained the annulated phosphiranes, leading to a number of structural distortions and selective decomplexation by CO under pressure. Chapter two also recounts the serendipitous discovery of phosphorus dimers from the thermolysis of 7-allyl-7-phosphanorbornadiene complex. Chapter three illustrates the study on the activation of 1-chlorophosphirane by aluminium trichloride. The subject of the study is cyclohexane-annulated 1-chlorophosphirane complex. It undergoes aluminium trichloride-catalysed electrophilic aromatic substitution with thiophene and ferrocene to produce 1-(2-thienyl)- and 1-ferrocenylphosphirane complexes respectively. In the absence of electron-rich arenes, a P-C bond cleavage catalysed by aluminium trichloride takes place yielding dichloro(cyclohexyl)phosphine complex. The transient ferrocenylphosphinidene complex can be generated from 1-ferrocenylphosphirane complex and trapped with diphenylacetylene, trans-stilbene and water.