University of Illinois Urbana-Champaign

Multifrequency Electron Paramagnetic Resonance Spectroscopy of Group Viib Carbonyl Radicals

Rattinger, Gail Beth

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Description

Title
Multifrequency Electron Paramagnetic Resonance Spectroscopy of Group Viib Carbonyl Radicals
Author(s)
Rattinger, Gail Beth
Issue Date
1984
Department of Study
Chemistry
Discipline
Chemistry
Degree Granting Institution
University of Illinois at Urbana-Champaign
Degree Name
Ph.D.
Degree Level
Dissertation
Keyword(s)
Chemistry, Inorganic
Abstract
  • Interest in organometallic 17e('-) free radical systems has increased dramatically due to their potential roles in catalytic processes. Multi-frequency electron paramagnetic resonance spectroscopy studies of (.)Mn(CO)(,3){P(n-Bu)(,3)}(,2), (.)Mn(CO)(,3){P(i-Bu)(,3)}(,2), (.)Mn(CO)(,3){P(i-Pr)(,3)}(,2') (.)Mn(CO)(,3){P(O-i-Pr)(,3)}(,2) and (.)Re(CO)(,3){P(cy)(,3)}(,2) (cy = cyclohexyl) were performed at conventional X-band ((DBLTURN) 9 GHz), S-band ((DBLTURN) 3 GHz) and L-band ((DBLTURN) 1 GHz) frequencies. Computer simulations of the X- and S-band frozen solution spectra as well as room temperature X-band solution spectra were obtained. Anisotropic g-shifts, metal hyperfine, and phosphorus super-hyperfine spin Hamiltonian parameters are reported and compared to values reported for (.)Mn(CO)(,5).
  • A perturbation treatment is developed and used in the interpretation of the anisotropic metal center parameters obtained for these square pyramidal d('7) systems. Information about the distribution of unpaired spin density is obtained. Variation of ligand steric and electronic parameters does not drastically vary the amount of unpaired spin density in the manganese 3d(,z)('2) orbital. Only a small percentage of unpaired spin density is found to be delocalized onto the phosphorus ligands. Upper and lower limits of core polarization as well as the energy difference, (DELTA)E, between the ground state and d(pi) excited state are estimated. Kinetics implications are discussed.
Graduation Semester
1984
Type of Resource
text
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http://hdl.handle.net/2142/70281

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