{"id":{"repo_id":"alabama","oai_identifier":"oai:ir.ua.edu:123456789/7854"},"canonical_url":"https://search.dev.ndltd.org/etd/alabama/oai:ir.ua.edu:123456789/7854","repository":{"repo_id":"alabama","name":"University of Alabama","base_url":"https://ir-api.ua.edu/oai/request"},"display":{"title":"Nitrosoarenes: magnetic anisotropy, donor-acceptor bonding and host-guest chemistry","abstract":"Nitrosoarenes (Ar-N=O) were first reported by Baeyer in 1874 after successful synthesis of nitrosobenzene via a diphenyl mercury reaction with nitrosyl bromide. C-nitroso compounds (R-N=O), like nitrosobenzene, fall between hydroxylamines (R-NH-OH) and nitro compounds (R-NO2) on the amine oxidation scale making them common intermediates for many synthetic amine oxidation reactions. Nitrosobenzenes exhibit a number of unique properties, which stem from their structure. A small energy gap between the HOMO (n*) and LUMO (?*) orbitals of the N=O function allows for several unique chemical and spectroscopic properties of nitrosoarenes. Nitrosobenzene and its derivatives have a blue-green color in monomeric form and reversibly dimerize to a colorless form in the solid state, thus yielding a dynamic covalent bonding reaction for this class of compounds. One area of our studies focuses on the very large (2-3 ppm) magnetic anisotropy of the nitroso group, which is evaluated for a series of ortho-substituted nitrosoarenes. The nitroso (-N=O) functions of these molecules are sterically forced into a primary (majority) orientation in the molecule by the ortho substituent, thereby allowing the NMR analysis of the magnetic environment around an oriented -N=O group at room temperature. Multiple substrates have been synthesized, including oriented 1,3-(bis)nitroso compounds, which have double the amount of shielding of the “syn” proton. A series of NMR techniques is employed to prove the NMR signal assignments for these compounds including: 1H, 13C, NOE, COSY, HSQC, and HMBC NMR spectroscopy. Also studied is the electron donor-acceptor (DA) bonding ability of the N=O group of N,N-dimethyl-4-nitrosobenzene (DMANB) and N,N-diethyl-4-nitrosobenzene (DEANB), in the monomeric state, as they complex and co-crystallize with electron-poor alkenes such as 2,3-dichloro-5,6-dicyano-1,4-benzoquinone (DDQ) and tetracyanoethylene (TCNE). Finally, encapsulation of N,N-dimethyl-4-nitrosobenzene (DMANB) and p-nitrosocumene (p-NC) by organic host molecules such as octa-acid (OA), cucurbit[7]uril (CB7), and cyclodextrins (?,?,?-cd) in aqueous solution is studied.","abstract_html":"Nitrosoarenes (Ar-N=O) were first reported by Baeyer in 1874 after successful synthesis of nitrosobenzene via a diphenyl mercury reaction with nitrosyl bromide. C-nitroso compounds (R-N=O), like nitrosobenzene, fall between hydroxylamines (R-NH-OH) and nitro compounds (R-NO2) on the amine oxidation scale making them common intermediates for many synthetic amine oxidation reactions. Nitrosobenzenes exhibit a number of unique properties, which stem from their structure. A small energy gap between the HOMO (n*) and LUMO (?*) orbitals of the N=O function allows for several unique chemical and spectroscopic properties of nitrosoarenes. Nitrosobenzene and its derivatives have a blue-green color in monomeric form and reversibly dimerize to a colorless form in the solid state, thus yielding a dynamic covalent bonding reaction for this class of compounds. One area of our studies focuses on the very large (2-3 ppm) magnetic anisotropy of the nitroso group, which is evaluated for a series of ortho-substituted nitrosoarenes. The nitroso (-N=O) functions of these molecules are sterically forced into a primary (majority) orientation in the molecule by the ortho substituent, thereby allowing the NMR analysis of the magnetic environment around an oriented -N=O group at room temperature. Multiple substrates have been synthesized, including oriented 1,3-(bis)nitroso compounds, which have double the amount of shielding of the “syn” proton. A series of NMR techniques is employed to prove the NMR signal assignments for these compounds including: 1H, 13C, NOE, COSY, HSQC, and HMBC NMR spectroscopy. Also studied is the electron donor-acceptor (DA) bonding ability of the N=O group of N,N-dimethyl-4-nitrosobenzene (DMANB) and N,N-diethyl-4-nitrosobenzene (DEANB), in the monomeric state, as they complex and co-crystallize with electron-poor alkenes such as 2,3-dichloro-5,6-dicyano-1,4-benzoquinone (DDQ) and tetracyanoethylene (TCNE). Finally, encapsulation of N,N-dimethyl-4-nitrosobenzene (DMANB) and p-nitrosocumene (p-NC) by organic host molecules such as octa-acid (OA), cucurbit[7]uril (CB7), and cyclodextrins (?,?,?-cd) in aqueous solution is studied.","abstract_has_math":false,"creators":["Kelley, Sarah Ariel"],"institution":"University of Alabama Libraries","degree_name":null,"degree_level":null,"degree_discipline":null,"degree_department":null,"school":null,"contributors":["Shaughnessy, Kevin H.","Jennings, Michael P.","Papish, Elizabeth T.","Pigza, Julie A."],"advisors":["Blackstock, Silas C."],"committee_chairs":[],"committee_members":[],"year":2021,"date_issued":"2021","date_published":"2021","updated_at":"2026-07-27T18:44:23Z","subjects":["Chemistry"],"languages":["en_US","English"],"rights":["All rights reserved by the author unless otherwise indicated."],"rights_urls":[],"identifier_entries":[{"key":"dc:identifier.other","label":"Dc Identifier Other","values":["u0015_0000001_0003775","Kelley_alatus_0004D_14473"],"render_values":[{"text":"u0015_0000001_0003775","href":null,"code":true},{"text":"Kelley_alatus_0004D_14473","href":null,"code":true}]}]},"links":{"outbound_url":"http://ir.ua.edu/handle/123456789/7854","outbound_label":"Repository record","outbound_source":"dc:identifier.uri"},"metadata_groups":[{"id":"people","label":"People","entries":[{"key":"dc:contributor","label":"Contributor","values":["Shaughnessy, Kevin H.","Jennings, Michael P.","Papish, Elizabeth T.","Pigza, Julie A."]},{"key":"dc:contributor.advisor","label":"Advisor","values":["Blackstock, Silas C."]},{"key":"dc:contributor.other","label":"Dc Contributor Other","values":["University of Alabama Tuscaloosa"]},{"key":"dc:creator","label":"Author","values":["Kelley, Sarah Ariel"]}]},{"id":"academic_context","label":"Academic Context","entries":[{"key":"dc:date.accessioned","label":"Dc Date Accessioned","values":["2021-07-07T14:36:45Z"]},{"key":"dc:date.available","label":"Dc Date Available","values":["2021-07-07T14:36:45Z"]},{"key":"dc:date.issued","label":"Date","values":["2021"]},{"key":"dc:publisher","label":"Institution","values":["University of Alabama Libraries"]},{"key":"dc:type","label":"Dc Type","values":["thesis","text"]}]},{"id":"subjects_keywords","label":"Subjects and Keywords","entries":[{"key":"dc:subject","label":"Dc Subject","values":["Chemistry"]}]},{"id":"language_rights","label":"Language and Rights","entries":[{"key":"dc:language","label":"Dc Language","values":["English"]},{"key":"dc:language.iso","label":"Language (ISO)","values":["en_US"]},{"key":"dc:rights","label":"Dc Rights","values":["All rights reserved by the author unless otherwise indicated."]}]},{"id":"identifiers","label":"Identifiers","entries":[{"key":"dc:identifier.other","label":"Dc Identifier Other","values":["u0015_0000001_0003775","Kelley_alatus_0004D_14473"]},{"key":"dc:identifier.uri","label":"Identifier URI","values":["http://ir.ua.edu/handle/123456789/7854"]}]},{"id":"additional","label":"Additional Metadata","entries":[{"key":"dc:description","label":"Description","values":["Electronic Thesis or Dissertation"]},{"key":"dc:description.abstract","label":"Abstract","values":["Nitrosoarenes (Ar-N=O) were first reported by Baeyer in 1874 after successful synthesis of nitrosobenzene via a diphenyl mercury reaction with nitrosyl bromide. C-nitroso compounds (R-N=O), like nitrosobenzene, fall between hydroxylamines (R-NH-OH) and nitro compounds (R-NO2) on the amine oxidation scale making them common intermediates for many synthetic amine oxidation reactions. Nitrosobenzenes exhibit a number of unique properties, which stem from their structure. A small energy gap between the HOMO (n*) and LUMO (?*) orbitals of the N=O function allows for several unique chemical and spectroscopic properties of nitrosoarenes. Nitrosobenzene and its derivatives have a blue-green color in monomeric form and reversibly dimerize to a colorless form in the solid state, thus yielding a dynamic covalent bonding reaction for this class of compounds. One area of our studies focuses on the very large (2-3 ppm) magnetic anisotropy of the nitroso group, which is evaluated for a series of ortho-substituted nitrosoarenes. The nitroso (-N=O) functions of these molecules are sterically forced into a primary (majority) orientation in the molecule by the ortho substituent, thereby allowing the NMR analysis of the magnetic environment around an oriented -N=O group at room temperature. Multiple substrates have been synthesized, including oriented 1,3-(bis)nitroso compounds, which have double the amount of shielding of the “syn” proton. A series of NMR techniques is employed to prove the NMR signal assignments for these compounds including: 1H, 13C, NOE, COSY, HSQC, and HMBC NMR spectroscopy. Also studied is the electron donor-acceptor (DA) bonding ability of the N=O group of N,N-dimethyl-4-nitrosobenzene (DMANB) and N,N-diethyl-4-nitrosobenzene (DEANB), in the monomeric state, as they complex and co-crystallize with electron-poor alkenes such as 2,3-dichloro-5,6-dicyano-1,4-benzoquinone (DDQ) and tetracyanoethylene (TCNE). Finally, encapsulation of N,N-dimethyl-4-nitrosobenzene (DMANB) and p-nitrosocumene (p-NC) by organic host molecules such as octa-acid (OA), cucurbit[7]uril (CB7), and cyclodextrins (?,?,?-cd) in aqueous solution is studied."]},{"key":"dc:format.medium","label":"Dc Format Medium","values":["electronic"]},{"key":"dc:format.mimetype","label":"Dc Format Mimetype","values":["application/pdf"]},{"key":"dc:title","label":"Title","values":["Nitrosoarenes: magnetic anisotropy, donor-acceptor bonding and host-guest chemistry"]}]}],"canonical_facts":{"dc:contributor":["Shaughnessy, Kevin H.","Jennings, Michael P.","Papish, Elizabeth T.","Pigza, Julie A."],"dc:contributor.advisor":["Blackstock, Silas C."],"dc:contributor.other":["University of Alabama Tuscaloosa"],"dc:creator":["Kelley, Sarah Ariel"],"dc:date.accessioned":["2021-07-07T14:36:45Z"],"dc:date.available":["2021-07-07T14:36:45Z"],"dc:date.issued":["2021"],"dc:description":["Electronic Thesis or Dissertation"],"dc:description.abstract":["Nitrosoarenes (Ar-N=O) were first reported by Baeyer in 1874 after successful synthesis of nitrosobenzene via a diphenyl mercury reaction with nitrosyl bromide. C-nitroso compounds (R-N=O), like nitrosobenzene, fall between hydroxylamines (R-NH-OH) and nitro compounds (R-NO2) on the amine oxidation scale making them common intermediates for many synthetic amine oxidation reactions. Nitrosobenzenes exhibit a number of unique properties, which stem from their structure. A small energy gap between the HOMO (n*) and LUMO (?*) orbitals of the N=O function allows for several unique chemical and spectroscopic properties of nitrosoarenes. Nitrosobenzene and its derivatives have a blue-green color in monomeric form and reversibly dimerize to a colorless form in the solid state, thus yielding a dynamic covalent bonding reaction for this class of compounds. One area of our studies focuses on the very large (2-3 ppm) magnetic anisotropy of the nitroso group, which is evaluated for a series of ortho-substituted nitrosoarenes. The nitroso (-N=O) functions of these molecules are sterically forced into a primary (majority) orientation in the molecule by the ortho substituent, thereby allowing the NMR analysis of the magnetic environment around an oriented -N=O group at room temperature. Multiple substrates have been synthesized, including oriented 1,3-(bis)nitroso compounds, which have double the amount of shielding of the “syn” proton. A series of NMR techniques is employed to prove the NMR signal assignments for these compounds including: 1H, 13C, NOE, COSY, HSQC, and HMBC NMR spectroscopy. Also studied is the electron donor-acceptor (DA) bonding ability of the N=O group of N,N-dimethyl-4-nitrosobenzene (DMANB) and N,N-diethyl-4-nitrosobenzene (DEANB), in the monomeric state, as they complex and co-crystallize with electron-poor alkenes such as 2,3-dichloro-5,6-dicyano-1,4-benzoquinone (DDQ) and tetracyanoethylene (TCNE). Finally, encapsulation of N,N-dimethyl-4-nitrosobenzene (DMANB) and p-nitrosocumene (p-NC) by organic host molecules such as octa-acid (OA), cucurbit[7]uril (CB7), and cyclodextrins (?,?,?-cd) in aqueous solution is studied."],"dc:format.medium":["electronic"],"dc:format.mimetype":["application/pdf"],"dc:identifier.other":["u0015_0000001_0003775","Kelley_alatus_0004D_14473"],"dc:identifier.uri":["http://ir.ua.edu/handle/123456789/7854"],"dc:language":["English"],"dc:language.iso":["en_US"],"dc:publisher":["University of Alabama Libraries"],"dc:rights":["All rights reserved by the author unless otherwise indicated."],"dc:subject":["Chemistry"],"dc:title":["Nitrosoarenes: magnetic anisotropy, donor-acceptor bonding and host-guest chemistry"],"dc:type":["thesis","text"]},"updated_at":"2026-07-27T18:44:23Z"}