M.Sc. / The main objective of the work presented in this dissertation was to investigate the application of the phosphorus atom as a probe to evaluate stereo-electronic effects in arylphosphines. Traditionally, electronic effects are described as having inductive or resonance origins. In addition to the aforementioned mechanisms, the possibility of an additional field effect pathway was also investigated. For this purpose, a series of ortho, meta and para mono-substituted triaryl phosphines, i.e. Ph2(C6H4-X), were synthesised using a lithium-halogen exchange pathway. This series included a selection of electron-withdrawing and electron-donating substituents (X = F, CN, COOtBu, Me, OMe, NMe2) as well as combinations of these. Most of these ligands are crystalline which allowed analysis of their electronic nature by means of X-ray crystallography. From these ligands a representative range of electron-donating and electron-withdrawing aryl substituted phosphines was chosen to collect high-resolution (d=0.5 Å) data. An aspherical multipole refinement was carried out on each of the high-resolution data sets by employing the Hansen Coppens multipole formalism. This was followed by an experimental charge density analysis of each phosphine by employing the principles of QTAIM employed in WinXD. From topological analysis of the Laplacian of the electron density, properties at the (3,-3) lone pair critical points were evaluated. Similarly, the density properties at the (3,-1) bond critical points of the P-Cipso bond were evaluated by analysis of the topology of the electron density. In addition, several integrated properties including the volume, charge and electron population of the phosphorus atom were evaluated. All of the above properties showed very good linear correlations with the infrared CO stretching frequencies of the Rh-Vaska-type complexes corresponding to these phosphines. Furthermore, computational chemistry was employed as a complementary investigation tool to the X-ray crystallographic study. A theoretical charge density study was conducted for the complete range of phosphines described above in paragraph 1 of this Synopsis by employing the principles of QTAIM employed in AIMAll. All of the properties mentioned in the above paragraph were also calculated. In addition, the calculated molecular electrostatic potential properties of the phosphorus lone pair (Vmin and dcp), the integrated substituent bond dipole and NBO (Natural bond orbital) analysis was used to evaluate substituent electronic effects. All of the calculated properties (with the exception of the charge and electron population of the phosphorus atom calculated from NBO analysis) showed good linear correlations with the infrared CO stretching frequencies of the Vaska-type complexes corresponding to these phosphines within a particular electron-withdrawing/electron-donating or ortho/meta and para series. In addition, very ii good linear correlations were obtained between the experimental and theoretical properties within a particular electron-withdrawing/electron-donating or ortho/meta and para series. As additional investigation tools, the ligands were characterised by several techniques including infrared CO stretching frequency measurements performed on Rh Vaska-type compounds derived from the synthesised ligands, 31P NMR chemical shift measurements as well as 103Rh-31P coupling constant measurements to evaluate the effect of various substituents on the electron density at the phosphorus lone pair. In conclusion, it was found that the phosphorus atom is a sensitive probe of substituent electronic effects. Furthermore, it was found that high-resolution X-ray crystallography, computational chemistry, 31P NMR and infrared spectroscopy are all excellent techniques that can be employed to obtain a better understanding of the nature and transmission of substituent effects. From this study, it appeared that the electronic effects in phosphine ligands could not be rationalised by an inductive mechanism alone, but seemingly more correctly by an additional field effect mechanism.
| Identifer | oai:union.ndltd.org:netd.ac.za/oai:union.ndltd.org:uj/uj:2925 |
| Date | 21 August 2012 |
| Creators | Renison, Carina Alicia |
| Source Sets | South African National ETD Portal |
| Detected Language | English |
| Type | Thesis |
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