{"id":{"repo_id":"mit","oai_identifier":"oai:dspace.mit.edu:1721.1/152129"},"canonical_url":"https://search.dev.ndltd.org/etd/mit/oai:dspace.mit.edu:1721.1/152129","repository":{"repo_id":"mit","name":"MIT","base_url":"https://dspace.mit.edu/oai/request"},"display":{"title":"Synthesis and Reactivity of Anthracene-Based Molecular Precursors for Low-Valent Boron Species","abstract":"The study of compounds containing elusive main group multiple bonds has long been a topic of immense interest. Today, it remains an attractive path towards unlocking new reactivity and developing a complete empirical understanding of chemical bonding. However, due in large part to a lack of suitable synthetic methodologies, the chemistry of numerous desirable functionalities remains poorly accessible. Herein, we report the synthesis of the first series of dibenzo-7-boranorbornadienes, or 9,10-bridged boron anthracene (RBA, A = anthracene or C₁₄H₁₀) compounds, and their unique properties and reactivity. Oxidation of ⁱPr₂NBA with an amine oxide was found to lead to the selective formation of the bicyclic borinate ester ⁱPr₂NBOA, an easily isolable solid that unimolecularly fragments to ⁱPr₂NBO + A upon heating to moderate temperatures in solution. This rare free, monomeric oxoborane has been demonstrated to undergo cycloadditions with a number of organic substrates and efforts to expand both the scope of derivatives and reactivity are underway. The possibility to access species containing highly unstable boron-pnictogen triple bonds has also been explored via the synthesis of the azidoborane trimer (N₃BA)₃ and cyclic(alkyl)(amino)carbene (CAAC) stabilized boraphosphaketene ᵉᵗCAAC·ABPCO. Preliminary and ongoing reactivity studies are discussed.","abstract_html":"The study of compounds containing elusive main group multiple bonds has long been a topic of immense interest. Today, it remains an attractive path towards unlocking new reactivity and developing a complete empirical understanding of chemical bonding. However, due in large part to a lack of suitable synthetic methodologies, the chemistry of numerous desirable functionalities remains poorly accessible. Herein, we report the synthesis of the first series of dibenzo-7-boranorbornadienes, or 9,10-bridged boron anthracene (RBA, A = anthracene or C₁₄H₁₀) compounds, and their unique properties and reactivity. Oxidation of ⁱPr₂NBA with an amine oxide was found to lead to the selective formation of the bicyclic borinate ester ⁱPr₂NBOA, an easily isolable solid that unimolecularly fragments to ⁱPr₂NBO + A upon heating to moderate temperatures in solution. This rare free, monomeric oxoborane has been demonstrated to undergo cycloadditions with a number of organic substrates and efforts to expand both the scope of derivatives and reactivity are underway. The possibility to access species containing highly unstable boron-pnictogen triple bonds has also been explored via the synthesis of the azidoborane trimer (N₃BA)₃ and cyclic(alkyl)(amino)carbene (CAAC) stabilized boraphosphaketene ᵉᵗCAAC·ABPCO. Preliminary and ongoing reactivity studies are discussed.","abstract_has_math":false,"creators":["Sukhram, Dion S."],"institution":"Massachusetts Institute of Technology","degree_name":"Bachelor","degree_level":null,"degree_discipline":null,"degree_department":"Massachusetts Institute of Technology. Department of Chemistry","school":null,"contributors":[],"advisors":["Cummins, Christopher C."],"committee_chairs":[],"committee_members":[],"year":2023,"date_issued":"2023-06","date_published":"2023-06","updated_at":"2026-07-22T22:21:19Z","subjects":[],"languages":[],"rights":["In Copyright - Educational Use Permitted","Copyright retained by author(s)"],"rights_urls":["https://rightsstatements.org/page/InC-EDU/1.0/"],"identifier_entries":[]},"links":{"outbound_url":"https://hdl.handle.net/1721.1/152129","outbound_label":"Handle","outbound_source":"dc:identifier.uri"},"metadata_groups":[{"id":"people","label":"People","entries":[{"key":"dc:contributor.advisor","label":"Advisor","values":["Cummins, Christopher C."]},{"key":"dc:contributor.department","label":"Department","values":["Massachusetts Institute of Technology. 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Today, it remains an attractive path towards unlocking new reactivity and developing a complete empirical understanding of chemical bonding. However, due in large part to a lack of suitable synthetic methodologies, the chemistry of numerous desirable functionalities remains poorly accessible. Herein, we report the synthesis of the first series of dibenzo-7-boranorbornadienes, or 9,10-bridged boron anthracene (RBA, A = anthracene or C₁₄H₁₀) compounds, and their unique properties and reactivity. Oxidation of ⁱPr₂NBA with an amine oxide was found to lead to the selective formation of the bicyclic borinate ester ⁱPr₂NBOA, an easily isolable solid that unimolecularly fragments to ⁱPr₂NBO + A upon heating to moderate temperatures in solution. This rare free, monomeric oxoborane has been demonstrated to undergo cycloadditions with a number of organic substrates and efforts to expand both the scope of derivatives and reactivity are underway. The possibility to access species containing highly unstable boron-pnictogen triple bonds has also been explored via the synthesis of the azidoborane trimer (N₃BA)₃ and cyclic(alkyl)(amino)carbene (CAAC) stabilized boraphosphaketene ᵉᵗCAAC·ABPCO. Preliminary and ongoing reactivity studies are discussed."]},{"key":"dc:description.degree","label":"Dc Description Degree","values":["S.B."]},{"key":"dc:title","label":"Title","values":["Synthesis and Reactivity of Anthracene-Based Molecular Precursors for Low-Valent Boron Species"]}]}],"canonical_facts":{"dc:contributor.advisor":["Cummins, Christopher C."],"dc:contributor.department":["Massachusetts Institute of Technology. Department of Chemistry"],"dc:creator":["Sukhram, Dion S."],"dc:date.accessioned":["2023-09-13T18:07:13Z"],"dc:date.available":["2023-09-13T18:07:13Z"],"dc:date.issued":["2023-06"],"dc:description.abstract":["The study of compounds containing elusive main group multiple bonds has long been a topic of immense interest. Today, it remains an attractive path towards unlocking new reactivity and developing a complete empirical understanding of chemical bonding. However, due in large part to a lack of suitable synthetic methodologies, the chemistry of numerous desirable functionalities remains poorly accessible. Herein, we report the synthesis of the first series of dibenzo-7-boranorbornadienes, or 9,10-bridged boron anthracene (RBA, A = anthracene or C₁₄H₁₀) compounds, and their unique properties and reactivity. Oxidation of ⁱPr₂NBA with an amine oxide was found to lead to the selective formation of the bicyclic borinate ester ⁱPr₂NBOA, an easily isolable solid that unimolecularly fragments to ⁱPr₂NBO + A upon heating to moderate temperatures in solution. This rare free, monomeric oxoborane has been demonstrated to undergo cycloadditions with a number of organic substrates and efforts to expand both the scope of derivatives and reactivity are underway. The possibility to access species containing highly unstable boron-pnictogen triple bonds has also been explored via the synthesis of the azidoborane trimer (N₃BA)₃ and cyclic(alkyl)(amino)carbene (CAAC) stabilized boraphosphaketene ᵉᵗCAAC·ABPCO. Preliminary and ongoing reactivity studies are discussed."],"dc:description.degree":["S.B."],"dc:identifier.uri":["https://hdl.handle.net/1721.1/152129"],"dc:publisher":["Massachusetts Institute of Technology"],"dc:rights":["In Copyright - Educational Use Permitted","Copyright retained by author(s)"],"dc:rights.uri":["https://rightsstatements.org/page/InC-EDU/1.0/"],"dc:title":["Synthesis and Reactivity of Anthracene-Based Molecular Precursors for Low-Valent Boron Species"],"dc:type":["Thesis"],"thesis:degree_name":["Bachelor","Bachelor of Science in Chemistry"]},"updated_at":"2026-07-22T22:21:19Z"}