{"id":{"repo_id":"uiuc","oai_identifier":"oai:www.ideals.illinois.edu:2142/67233"},"canonical_url":"https://search.dev.ndltd.org/etd/uiuc/oai:www.ideals.illinois.edu:2142/67233","repository":{"repo_id":"uiuc","name":"University of Illinois - Urbana-Champaign","base_url":"https://www.ideals.illinois.edu/oai-pmh"},"display":{"title":"Synthesis and Properties of Ortho-Bridged Triarylmethyl Compounds","abstract":"The stable carbocation salts 2-tert-butylsesquixanthydryl triflate (2-tert-butyl-4,8,12-trioxadibenzo{cd,mn}pyrenyl trifluoromethanesulfonate) (Ia) and 2,6,10-tri-tert-butylsesquixanthydryl triflate (Ib) are found to be highly delocalized by ('13)C NMR as is expected based on the HMO calculation.","abstract_html":"The stable carbocation salts 2-tert-butylsesquixanthydryl triflate (2-tert-butyl-4,8,12-trioxadibenzo{cd,mn}pyrenyl trifluoromethanesulfonate) (Ia) and 2,6,10-tri-tert-butylsesquixanthydryl triflate (Ib) are found to be highly delocalized by ('13)C NMR as is expected based on the HMO calculation.","abstract_has_math":false,"creators":["Peters, Norman John"],"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":"2014-12-13T20:10:58Z","date_published":"2014-12-13T20:10:58Z","updated_at":"2026-07-22T22:25:57Z","subjects":["Chemistry, Organic"],"languages":["eng"],"rights":[],"rights_urls":[],"identifier_entries":[{"key":"dc:identifier","label":"Identifier","values":["(UMI)AAI8026571"],"render_values":[{"text":"(UMI)AAI8026571","href":null,"code":true}]}]},"links":{"outbound_url":"http://hdl.handle.net/2142/67233","outbound_label":"Handle","outbound_source":"dc:identifier"},"metadata_groups":[{"id":"people","label":"People","entries":[{"key":"dc:creator","label":"Author","values":["Peters, Norman John"]}]},{"id":"academic_context","label":"Academic Context","entries":[{"key":"dc:date","label":"Dc Date","values":["2014-12-13T20:10:58Z","10000-01-01","1980"]},{"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, Organic"]}]},{"id":"language_rights","label":"Language and Rights","entries":[{"key":"dc:language","label":"Dc Language","values":["eng"]}]},{"id":"identifiers","label":"Identifiers","entries":[{"key":"dc:identifier","label":"Identifier","values":["http://hdl.handle.net/2142/67233","(UMI)AAI8026571"]}]},{"id":"additional","label":"Additional Metadata","entries":[{"key":"dc:description","label":"Description","values":["The stable carbocation salts 2-tert-butylsesquixanthydryl triflate (2-tert-butyl-4,8,12-trioxadibenzo{cd,mn}pyrenyl trifluoromethanesulfonate) (Ia) and 2,6,10-tri-tert-butylsesquixanthydryl triflate (Ib) are found to be highly delocalized by ('13)C NMR as is expected based on the HMO calculation.","Ia R = H IIa R = H","Ib R = C(CH(,3))(,3) IIb R = C(CH(,3))(,3)","The tert-butylsesquixanthydryl dimers IIa and IIb are vastly more soluble than the unsubstituted dimer. Dimer IIb is only slightly dissociated in solution and reacts only slowly with oxygen. This suggests that the dissociation of the dimer into free radicals is both thermodynamically unfavored and slow despite the possibility of the radical being highly stabilized by delocalization. The dimers are shown to be hexaarylethanes by ('1)H and ('13)C NMR. The X-ray crystal structure of IIa reveals an unusually long C(,ethane)-C(,ethane) bond (1.63 (ANGSTROM)) and short C(,ethane)-C(,phenyl) bonds (1.49 (ANGSTROM)) which may be due to throughbond coupling of the (sigma) and (pi) orbitals.","Dimer IIb forms a novel crystalline complex with triflate Ib (1:2). The complex is too weakly associated to be observed in solution and forms crystals too small to be useful for X-ray crystallography. The bonding in this dimer therefore remains undetermined. The small (2%) number of unpaired electrons determined by electron spin resonance spectroscopy suggests that the bonding is extensively delocalized rather than being sesquixanthydryl moieties held together by a one-electron bond.","Made available in DSpace on 2014-12-13T20:10:58Z (GMT). No. of bitstreams: 1 8026571.pdf: 3338233 bytes, checksum: 0cb22a84ad57ac45d58127e1629052cb (MD5) Previous issue date: 1980","Embargo set by: Seth Robbins for item 67411 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","106 p.","Thesis (Ph.D.)--University of Illinois at Urbana-Champaign, 1980."]},{"key":"dc:title","label":"Title","values":["Synthesis and Properties of Ortho-Bridged Triarylmethyl Compounds"]}]}],"canonical_facts":{"dc:creator":["Peters, Norman John"],"dc:date":["2014-12-13T20:10:58Z","10000-01-01","1980"],"dc:description":["The stable carbocation salts 2-tert-butylsesquixanthydryl triflate (2-tert-butyl-4,8,12-trioxadibenzo{cd,mn}pyrenyl trifluoromethanesulfonate) (Ia) and 2,6,10-tri-tert-butylsesquixanthydryl triflate (Ib) are found to be highly delocalized by ('13)C NMR as is expected based on the HMO calculation.","Ia R = H IIa R = H","Ib R = C(CH(,3))(,3) IIb R = C(CH(,3))(,3)","The tert-butylsesquixanthydryl dimers IIa and IIb are vastly more soluble than the unsubstituted dimer. Dimer IIb is only slightly dissociated in solution and reacts only slowly with oxygen. This suggests that the dissociation of the dimer into free radicals is both thermodynamically unfavored and slow despite the possibility of the radical being highly stabilized by delocalization. The dimers are shown to be hexaarylethanes by ('1)H and ('13)C NMR. The X-ray crystal structure of IIa reveals an unusually long C(,ethane)-C(,ethane) bond (1.63 (ANGSTROM)) and short C(,ethane)-C(,phenyl) bonds (1.49 (ANGSTROM)) which may be due to throughbond coupling of the (sigma) and (pi) orbitals.","Dimer IIb forms a novel crystalline complex with triflate Ib (1:2). The complex is too weakly associated to be observed in solution and forms crystals too small to be useful for X-ray crystallography. The bonding in this dimer therefore remains undetermined. The small (2%) number of unpaired electrons determined by electron spin resonance spectroscopy suggests that the bonding is extensively delocalized rather than being sesquixanthydryl moieties held together by a one-electron bond.","Made available in DSpace on 2014-12-13T20:10:58Z (GMT). No. of bitstreams: 1 8026571.pdf: 3338233 bytes, checksum: 0cb22a84ad57ac45d58127e1629052cb (MD5) Previous issue date: 1980","Embargo set by: Seth Robbins for item 67411 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","106 p.","Thesis (Ph.D.)--University of Illinois at Urbana-Champaign, 1980."],"dc:identifier":["http://hdl.handle.net/2142/67233","(UMI)AAI8026571"],"dc:language":["eng"],"dc:subject":["Chemistry, Organic"],"dc:title":["Synthesis and Properties of Ortho-Bridged Triarylmethyl Compounds"],"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":"2026-07-22T22:25:57Z"}