Multifrequency Electron Paramagnetic Resonance Spectroscopy of Group Viib Carbonyl Radicals

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).

Name thesis:degree_name

Ph.D.

Level thesis:degree_level

Dissertation

Discipline thesis:degree_discipline

Chemistry

Grantor

University of Illinois at Urbana-Champaign

Year dc:date

2014

Author dc:creator

• Rattinger, Gail Beth

• Chemistry, Inorganic

Identifier

(UMI)AAI8502277

OAI identifier oai:identifier

oai:www.ideals.illinois.edu:2142/70281