{"id":{"repo_id":"uiuc","oai_identifier":"oai:www.ideals.illinois.edu:2142/70281"},"canonical_url":"https://search.dev.ndltd.org/etd/uiuc/oai:www.ideals.illinois.edu:2142/70281","repository":{"repo_id":"uiuc","name":"University of Illinois - Urbana-Champaign","base_url":"https://www.ideals.illinois.edu/oai-pmh"},"display":{"title":"Multifrequency Electron Paramagnetic Resonance Spectroscopy of Group Viib Carbonyl Radicals","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).","abstract_html":"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).","abstract_has_math":false,"creators":["Rattinger, Gail Beth"],"institution":"University of Illinois at Urbana-Champaign","degree_name":"Ph.D.","degree_level":"Dissertation","degree_discipline":"Chemistry","degree_department":null,"school":null,"contributors":[],"advisors":[],"committee_chairs":[],"committee_members":[],"year":2014,"date_issued":"2014-12-15T23:18:21Z","date_published":"2014-12-15T23:18:21Z","updated_at":"2026-07-22T22:26:02Z","subjects":["Chemistry, Inorganic"],"languages":[],"rights":[],"rights_urls":[],"identifier_entries":[{"key":"dc:identifier","label":"Identifier","values":["(UMI)AAI8502277"],"render_values":[{"text":"(UMI)AAI8502277","href":null,"code":true}]}]},"links":{"outbound_url":"http://hdl.handle.net/2142/70281","outbound_label":"Handle","outbound_source":"dc:identifier"},"metadata_groups":[{"id":"people","label":"People","entries":[{"key":"dc:creator","label":"Author","values":["Rattinger, Gail Beth"]}]},{"id":"academic_context","label":"Academic Context","entries":[{"key":"dc:date","label":"Dc Date","values":["2014-12-15T23:18:21Z","10000-01-01","1984"]},{"key":"dc:type","label":"Dc Type","values":["text"]},{"key":"thesis:degree_discipline","label":"Discipline","values":["Chemistry"]},{"key":"thesis:degree_level","label":"Degree Level","values":["Dissertation"]},{"key":"thesis:degree_name","label":"Degree Name","values":["Ph.D."]},{"key":"thesis:institution_name","label":"Thesis Institution Name","values":["University of Illinois at Urbana-Champaign"]}]},{"id":"subjects_keywords","label":"Subjects and Keywords","entries":[{"key":"dc:subject","label":"Dc Subject","values":["Chemistry, Inorganic"]}]},{"id":"identifiers","label":"Identifiers","entries":[{"key":"dc:identifier","label":"Identifier","values":["http://hdl.handle.net/2142/70281","(UMI)AAI8502277"]}]},{"id":"additional","label":"Additional Metadata","entries":[{"key":"dc:description","label":"Description","values":["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.","Made available in DSpace on 2014-12-15T23:18:21Z (GMT). No. of bitstreams: 1 8502277.pdf: 6507113 bytes, checksum: 71605a33a334259f908c2d78735c22f0 (MD5) Previous issue date: 1984","Embargo set by: Seth Robbins for item 70447 Lift date: Forever Reason: Restricted to the U of I community idenfinitely during batch ingest of legacy ETDs","Restricted to the U of I community idenfinitely during batch ingest of legacy ETDs","U of I Only","244 p.","Thesis (Ph.D.)--University of Illinois at Urbana-Champaign, 1984."]},{"key":"dc:title","label":"Title","values":["Multifrequency Electron Paramagnetic Resonance Spectroscopy of Group Viib Carbonyl Radicals"]}]}],"canonical_facts":{"dc:creator":["Rattinger, Gail Beth"],"dc:date":["2014-12-15T23:18:21Z","10000-01-01","1984"],"dc:description":["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.","Made available in DSpace on 2014-12-15T23:18:21Z (GMT). No. of bitstreams: 1 8502277.pdf: 6507113 bytes, checksum: 71605a33a334259f908c2d78735c22f0 (MD5) Previous issue date: 1984","Embargo set by: Seth Robbins for item 70447 Lift date: Forever Reason: Restricted to the U of I community idenfinitely during batch ingest of legacy ETDs","Restricted to the U of I community idenfinitely during batch ingest of legacy ETDs","U of I Only","244 p.","Thesis (Ph.D.)--University of Illinois at Urbana-Champaign, 1984."],"dc:identifier":["http://hdl.handle.net/2142/70281","(UMI)AAI8502277"],"dc:subject":["Chemistry, Inorganic"],"dc:title":["Multifrequency Electron Paramagnetic Resonance Spectroscopy of Group Viib Carbonyl Radicals"],"dc:type":["text"],"thesis:degree_discipline":["Chemistry"],"thesis:degree_level":["Dissertation"],"thesis:degree_name":["Ph.D."],"thesis:institution_name":["University of Illinois at Urbana-Champaign"]},"updated_at":"2026-07-22T22:26:02Z"}