{"id":{"repo_id":"baylor","oai_identifier":"oai:baylor-ir.tdl.org:2104/14084"},"canonical_url":"https://search.dev.ndltd.org/etd/baylor/oai:baylor-ir.tdl.org:2104/14084","repository":{"repo_id":"baylor","name":"Baylor University","base_url":"https://baylor-ir.tdl.org/server/oai/request"},"display":{"title":"Boron ligand design and reactivity in metal complexes.","abstract":"Boron-based compounds display diverse and tunable reactivity that makes them valuable building blocks for synthetic chemistry and materials design. This dissertation explores the reactivity of electrophilic boron species and their interplay with transition metals and carborane clusters, with an emphasis on uncovering fundamental bonding modes and divergent reaction pathways. The first portion examines hydroboration chemistry beyond conventional catalysis, highlighting the unique outcomes observed with metal acetylides. Copper acetylides favor alkynyl transfer to boranes, forming stable alkynylboronates, while gold acetylides exhibit distinct covalent bonding that directs reactivity along alternative pathways. These findings demonstrate how subtle differences in metal–acetylide bonding can drastically reshape product distributions in boron-mediated transformations. Building from small-molecule systems, the reactivity of carborane clusters is investigated through reduction and functionalization strategies. Potassium/18-crown-6 mediated reductions generate reactive boryl anions capable of engaging in cage C–H activation, enabling new B–C bond construction. Comparative studies with crown ether encapsulation reveal that cation–cage interactions directly influence structural distortions and cage opening, underscoring the importance of ion pairing in governing carborane reactivity. Finally, reductions of boron cluster complexes leading to nido-carborane and metallocarborane species expand the accessible chemical space of boron-rich frameworks, offering insights into electronic delocalization and metal–boron cooperation. Together, these investigations illustrate how the design of electrophilic boranes, in combination with transition metal or cluster frameworks, can be leveraged to achieve selective bond activation and novel molecular architectures. Overall, this work advances the understanding of boron reactivity across molecular and cluster domains, providing new strategies for manipulating structure, selectivity, and electronic properties in boron-rich systems.","abstract_html":"Boron-based compounds display diverse and tunable reactivity that makes them valuable building blocks for synthetic chemistry and materials design. This dissertation explores the reactivity of electrophilic boron species and their interplay with transition metals and carborane clusters, with an emphasis on uncovering fundamental bonding modes and divergent reaction pathways. The first portion examines hydroboration chemistry beyond conventional catalysis, highlighting the unique outcomes observed with metal acetylides. Copper acetylides favor alkynyl transfer to boranes, forming stable alkynylboronates, while gold acetylides exhibit distinct covalent bonding that directs reactivity along alternative pathways. These findings demonstrate how subtle differences in metal–acetylide bonding can drastically reshape product distributions in boron-mediated transformations. Building from small-molecule systems, the reactivity of carborane clusters is investigated through reduction and functionalization strategies. Potassium/18-crown-6 mediated reductions generate reactive boryl anions capable of engaging in cage C–H activation, enabling new B–C bond construction. Comparative studies with crown ether encapsulation reveal that cation–cage interactions directly influence structural distortions and cage opening, underscoring the importance of ion pairing in governing carborane reactivity. Finally, reductions of boron cluster complexes leading to nido-carborane and metallocarborane species expand the accessible chemical space of boron-rich frameworks, offering insights into electronic delocalization and metal–boron cooperation. Together, these investigations illustrate how the design of electrophilic boranes, in combination with transition metal or cluster frameworks, can be leveraged to achieve selective bond activation and novel molecular architectures. Overall, this work advances the understanding of boron reactivity across molecular and cluster domains, providing new strategies for manipulating structure, selectivity, and electronic properties in boron-rich systems.","abstract_has_math":false,"creators":["Thornton, Ragene A., 1996-"],"institution":"Baylor University.","degree_name":"Ph.D.","degree_level":"Doctoral","degree_discipline":null,"degree_department":null,"school":null,"contributors":[],"advisors":["Martin, Caleb D."],"committee_chairs":[],"committee_members":[],"year":2025,"date_issued":"2025-12","date_published":"2025-12","updated_at":"2026-07-24T01:08:00Z","subjects":["Carborane.","Boron.","Transition metals."],"languages":["en"],"rights":["Baylor University works are protected by copyright. They may be viewed from this source for any purpose, but reproduction or distribution in any format is prohibited without written permission. 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They may be viewed from this source for any purpose, but reproduction or distribution in any format is prohibited without written permission. Contact libraryquestions@baylor.edu for inquiries about permission."]}]},{"id":"identifiers","label":"Identifiers","entries":[{"key":"dc:identifier.uri","label":"Identifier URI","values":["https://hdl.handle.net/2104/14084"]}]},{"id":"additional","label":"Additional Metadata","entries":[{"key":"dc:description.abstract","label":"Abstract","values":["Boron-based compounds display diverse and tunable reactivity that makes them valuable building blocks for synthetic chemistry and materials design. This dissertation explores the reactivity of electrophilic boron species and their interplay with transition metals and carborane clusters, with an emphasis on uncovering fundamental bonding modes and divergent reaction pathways. The first portion examines hydroboration chemistry beyond conventional catalysis, highlighting the unique outcomes observed with metal acetylides. Copper acetylides favor alkynyl transfer to boranes, forming stable alkynylboronates, while gold acetylides exhibit distinct covalent bonding that directs reactivity along alternative pathways. These findings demonstrate how subtle differences in metal–acetylide bonding can drastically reshape product distributions in boron-mediated transformations. Building from small-molecule systems, the reactivity of carborane clusters is investigated through reduction and functionalization strategies. Potassium/18-crown-6 mediated reductions generate reactive boryl anions capable of engaging in cage C–H activation, enabling new B–C bond construction. Comparative studies with crown ether encapsulation reveal that cation–cage interactions directly influence structural distortions and cage opening, underscoring the importance of ion pairing in governing carborane reactivity. Finally, reductions of boron cluster complexes leading to nido-carborane and metallocarborane species expand the accessible chemical space of boron-rich frameworks, offering insights into electronic delocalization and metal–boron cooperation. Together, these investigations illustrate how the design of electrophilic boranes, in combination with transition metal or cluster frameworks, can be leveraged to achieve selective bond activation and novel molecular architectures. Overall, this work advances the understanding of boron reactivity across molecular and cluster domains, providing new strategies for manipulating structure, selectivity, and electronic properties in boron-rich systems."]},{"key":"dc:format.mimetype","label":"Dc Format Mimetype","values":["application/pdf"]},{"key":"dc:title","label":"Title","values":["Boron ligand design and reactivity in metal complexes."]}]}],"canonical_facts":{"dc:contributor.advisor":["Martin, Caleb D."],"dc:creator":["Thornton, Ragene A., 1996-"],"dc:date.accessioned":["2026-01-21T16:14:34Z"],"dc:date.issued":["2025-12"],"dc:description.abstract":["Boron-based compounds display diverse and tunable reactivity that makes them valuable building blocks for synthetic chemistry and materials design. This dissertation explores the reactivity of electrophilic boron species and their interplay with transition metals and carborane clusters, with an emphasis on uncovering fundamental bonding modes and divergent reaction pathways. The first portion examines hydroboration chemistry beyond conventional catalysis, highlighting the unique outcomes observed with metal acetylides. Copper acetylides favor alkynyl transfer to boranes, forming stable alkynylboronates, while gold acetylides exhibit distinct covalent bonding that directs reactivity along alternative pathways. These findings demonstrate how subtle differences in metal–acetylide bonding can drastically reshape product distributions in boron-mediated transformations. Building from small-molecule systems, the reactivity of carborane clusters is investigated through reduction and functionalization strategies. Potassium/18-crown-6 mediated reductions generate reactive boryl anions capable of engaging in cage C–H activation, enabling new B–C bond construction. Comparative studies with crown ether encapsulation reveal that cation–cage interactions directly influence structural distortions and cage opening, underscoring the importance of ion pairing in governing carborane reactivity. Finally, reductions of boron cluster complexes leading to nido-carborane and metallocarborane species expand the accessible chemical space of boron-rich frameworks, offering insights into electronic delocalization and metal–boron cooperation. Together, these investigations illustrate how the design of electrophilic boranes, in combination with transition metal or cluster frameworks, can be leveraged to achieve selective bond activation and novel molecular architectures. Overall, this work advances the understanding of boron reactivity across molecular and cluster domains, providing new strategies for manipulating structure, selectivity, and electronic properties in boron-rich systems."],"dc:format.mimetype":["application/pdf"],"dc:identifier.uri":["https://hdl.handle.net/2104/14084"],"dc:language.iso":["en"],"dc:rights":["Baylor University works are protected by copyright. They may be viewed from this source for any purpose, but reproduction or distribution in any format is prohibited without written permission. Contact libraryquestions@baylor.edu for inquiries about permission."],"dc:subject":["Carborane.","Boron.","Transition metals."],"dc:title":["Boron ligand design and reactivity in metal complexes."],"dc:type":["Thesis"],"thesis:degree_level":["Doctoral"],"thesis:degree_name":["Ph.D."],"thesis:institution_name":["Baylor University."]},"updated_at":"2026-07-24T01:08:00Z"}