Date of Award
1996
Degree Type
Dissertation
Degree Name
Doctor of Philosophy
Abstract
High resolution gas phase photoelectron spectra of transition metal carbonyls, W(CO){dollar}\sb6,{dollar} Os(CO){dollar}\sb4{dollar}L (L = CO, PMe{dollar}\sb3),{dollar} CpM(CO){dollar}\sb3{dollar} (M = Mn, Re), CpFe(CO){dollar}\sb2{dollar}I, and Re(CO){dollar}\sb5{dollar}X (X = Re(CO){dollar}\sb5,{dollar} Cl, Br, and I) are reported. The advantages of monochromatized synchrotron radiation for studying the electronic structure of organometallic molecules are demonstrated. All the levels of these metal carbonyls from valence to inner-valence and core levels at high resolution can be studied in one spectrum.;For the core levels, vibrational fine structure is clearly resolved for the first time on the core of W 4f levels of W(CO){dollar}\sb6,{dollar} and this structure can be rationalized using the core equivalent model. Ligand field splitting is also shown to be important in the line broadening of the high resolution Os and Re 4f level spectra. The core and valence level chemical shifts of Os(CO){dollar}\sb4{dollar}L and Re(CO){dollar}\sb5{dollar}X complexes are compared by using Jolly's treatment. The high intensity of synchotron radiation is important for observing the weak metal np core level spectra for the first time. The knowledge of the binding energies of the metal np levels is important for observing np {dollar}\to{dollar} nd resonances on the valence nd levels.;For the valence levels, the np {dollar}\to{dollar} nd resonance and the Cooper minimum effect are observed using variable energy photoelectron spectroscopy. The observation of these two effects provides firm assignments for the metal nd valence orbitals of all the metal carbonyls studied in this thesis. Vibrational fine structure is resolved on the 5d based peaks in the third row transition metal carbonyls. The X{dollar}\alpha{dollar}-SW calculations of Os(CO){dollar}\sb5{dollar} and CpMn(CO){dollar}\sb3{dollar} are used to aid in the complete valence level assignments of these molecules. The experimental branching ratios are found to be in good agreement with the theoretical results (by X{dollar}\alpha{dollar}-SW and Gelius treatment).;The high resolution and high intensity of synchotron radiation is critical for the study of the weak and broad inner-valence spectra of these metal carbonyls. The inner-valence level of these molecules is shown to be dominated by contributions from the CO group, with the exception of the P 3s orbital in Os(CO){dollar}\sb4{dollar}PMe{dollar}\sb3.{dollar}
Recommended Citation
Hu, Yongfeng, "Variable Energy Photoelectron Spectra Of Metal Carbonyls" (1996). Digitized Theses. 2700.
https://ir.lib.uwo.ca/digitizedtheses/2700