Coordination chemistry and catalytic applications of 2-phospinophosphinines

Abstract

This thesis details research undertaken into investigating the synthesis and coordination chemistry of phosphinophosphinines, as well as the usage of several complexes in a range of catalytic transformations. The results presented in chapter two are primarily based on the synthesis of new mono- and bis-phosphinophosphinines, as well as some derivatives, including the phosphineborane and selenide. Crystallographic data are presented for the key compounds, as prior to this research, such data had yet to be reported for underivatised or noncoordinated phosphinophosphinines. In chapter three, the reactivities of two phosphinophosphinines with group 6 [M(diene)(CO)4] fragments are described, and infrared spectroscopic data are utilised to facilitate comparisons between the donor properties of these ligands as well as more familiar P-donors. To aid in these comparisons, the two phosphinophosphinines (and several hypothetical analogues) were analysed computationally by Dr Natalie Fey at the University of Bristol using the P,P-donor Ligand Knowledge Base. Finally, in collaboration with Sasol UK, results obtained from the use of phosphinophosphinines in the catalytic oligomerisation of ethylene are presented. Finally, in chapters four and five, the coordination chemistries of a phosphinophosphinine to ruthenium and rhodium (respectively) precursor complexes are discussed. The resulting complexes are analysed in terms of their spectroscopic and structural data, as well as their activity as catalysts for a range of reactions.