| dc.contributor.author | Phillips, Andrew Douglas. | en_US |
| dc.date.accessioned | 2014-10-21T12:36:26Z | |
| dc.date.available | 2001 | |
| dc.date.issued | 2001 | en_US |
| dc.identifier.other | AAINQ66642 | en_US |
| dc.identifier.uri | http://hdl.handle.net/10222/55770 | |
| dc.description | Phosphines, where there is a lone pair of electrons on phosphorus, are typically regarded as Lewis bases, whereas hypervalent bonding environments with electronegative substituents are effective Lewis acids. The discovery of compounds with mono- and di-substituted phosphine centres, such as the phosphadiazonium cation Mes*NP+ (Mes* = 2,4,6-tri- tert-butylphenyl) and iminophosphines, RNPR', provide access to new phosphorus bonding environments. The complexes reported in this thesis represent the development of phosphines as Lewis acids. | en_US |
| dc.description | A series of phosphadiazonium-ligand-triflate complexes [Mes*NP•Lg]OSO 2CF3, (Lg = Ligand), (A) have been isolated and comprehensively characterized. This involved a series of ligands having a range of basicities and polarizabilities (pyridine, 1-azabicyclo[2.2.2]-octane, imidazol-2-ylidene, tertiary phosphine chalcogenides and chalcogenoimidazolines). Spectroscopic and structural properties of these complexes are discussed in the context of data available for other established bonding environments of phosphorus. A complex (B) containing a chelated phosphine centre has been prepared and characterized using the bidentate 2,2' -dipyridyl ligand. | en_US |
| dc.description | The synthesis of previously unknown P-functionalized iminophosphines (i.e., P-silyl-iminophosphines) was accomplished using Mes*NPOSO2CF3 as a Lewis acid. The Lewis acidic properties of P-chloro-iminophosphine (Mes*NPCl) have been demonstrated using imidazol-2-ylidene as a ligand affording a complex ( C) which represents a definitive example of an iminophosphide bonding environment. The adduct features a trisubstituted phosphorus centre with pyramidal geometry and P--N pi-bonding.* | en_US |
| dc.description | *Please refer to dissertation for diagrams. | en_US |
| dc.description | Thesis (Ph.D.)--Dalhousie University (Canada), 2001. | en_US |
| dc.language | eng | en_US |
| dc.publisher | Dalhousie University | en_US |
| dc.publisher | | en_US |
| dc.subject | Chemistry, Inorganic. | en_US |
| dc.title | Synthesis and characterization of complexes involving phosphino-centres as Lewis acids. | en_US |
| dc.type | text | en_US |
| dc.contributor.degree | Ph.D. | en_US |
