{"id":{"repo_id":"tuebingen","oai_identifier":"oai:publikationen.uni-tuebingen.de:10900/49632"},"canonical_url":"https://search.dev.ndltd.org/etd/tuebingen/oai:publikationen.uni-tuebingen.de:10900/49632","repository":{"repo_id":"tuebingen","name":"Universität Tübingen","base_url":"https://publikationen.uni-tuebingen.de/oai/request"},"display":{"title":"Boron-Nitrogen Derivatives of Organic Reactive Intermediates","abstract":"The boron-nitrogen derivatives of organic molecules have attracted the chemists’ attention due to their distinct chemical properties. This dissertation focuses on ways to access the diphenylaminoborylene (Ph2NB:) and 9,10-didehydro-9-aza-10-boraphenanthrene (E). The diphenylaminoborylene, is isostructural to vinylidene and that was intended to generate from bisazido(diphenylamino)borane [Ph2NB(N3)2] under matrix isolation condition. During sublimation an extremely dangerous and highly explosive triazidoborane [B(N3)3] was sublimed. Upon photolysis the corresponding photo product NNBN was identified. The BN derivative of o-benzyne is called 1,2-azaborine and 9,10-didehydro-9-aza-10-boraphenanthrene (E) is a higher analog of 1,2-azaborine. To obtain E, different routes have been followed: (i) thermolysis of azidoborane, (ii) thermolysis of silyl(silyloxy)aminoborole and (iii) base induced dehydrohalogenation. This research has produced a number of key findings: a new type of azidoborane is introduced and its cyclotrimerization due to high Lewis acidity is observed; formal dyotropic rearrangement of aminoborole to azaborine fragment is attained; dehydrohalogenation of appropriate aminoborane by suitable bases has been established.","abstract_html":"The boron-nitrogen derivatives of organic molecules have attracted the chemists’ attention due to their distinct chemical properties. This dissertation focuses on ways to access the diphenylaminoborylene (Ph2NB:) and 9,10-didehydro-9-aza-10-boraphenanthrene (E). The diphenylaminoborylene, is isostructural to vinylidene and that was intended to generate from bisazido(diphenylamino)borane [Ph2NB(N3)2] under matrix isolation condition. During sublimation an extremely dangerous and highly explosive triazidoborane [B(N3)3] was sublimed. Upon photolysis the corresponding photo product NNBN was identified. The BN derivative of o-benzyne is called 1,2-azaborine and 9,10-didehydro-9-aza-10-boraphenanthrene (E) is a higher analog of 1,2-azaborine. To obtain E, different routes have been followed: (i) thermolysis of azidoborane, (ii) thermolysis of silyl(silyloxy)aminoborole and (iii) base induced dehydrohalogenation. This research has produced a number of key findings: a new type of azidoborane is introduced and its cyclotrimerization due to high Lewis acidity is observed; formal dyotropic rearrangement of aminoborole to azaborine fragment is attained; dehydrohalogenation of appropriate aminoborane by suitable bases has been established.","abstract_has_math":false,"creators":["Biswas, Sunanda"],"institution":null,"degree_name":null,"degree_level":null,"degree_discipline":null,"degree_department":null,"school":null,"contributors":[],"advisors":[],"committee_chairs":[],"committee_members":[],"year":2012,"date_issued":"2012","date_published":"2012","updated_at":"2026-08-21T22:21:56Z","subjects":[],"languages":[],"rights":[],"rights_urls":[],"identifier_entries":[{"key":"dc:identifier","label":"Identifier","values":["hdl:10900/49632"],"render_values":[{"text":"hdl:10900/49632","href":null,"code":true}]}]},"links":{"outbound_url":null,"outbound_label":null,"outbound_source":null},"source_record":{"url":"https://publikationen.uni-tuebingen.de/oai/request?verb=GetRecord&metadataPrefix=mets&identifier=oai%3Apublikationen.uni-tuebingen.de%3A10900%2F49632","prefix":"mets"},"metadata_groups":[{"id":"academic_context","label":"Academic Context","entries":[{"key":"dc:date.issued","label":"Date","values":["2012"]},{"key":"dc:type","label":"Dc Type","values":["PhDThesis"]}]},{"id":"identifiers","label":"Identifiers","entries":[{"key":"dc:identifier","label":"Identifier","values":["hdl:10900/49632"]}]},{"id":"additional","label":"Additional Metadata","entries":[{"key":"dc:description.other","label":"Dc Description Other","values":["The boron-nitrogen derivatives of organic molecules have attracted the chemists’ attention due to their distinct chemical properties. This dissertation focuses on ways to access the diphenylaminoborylene (Ph2NB:) and 9,10-didehydro-9-aza-10-boraphenanthrene (E). The diphenylaminoborylene, is isostructural to vinylidene and that was intended to generate from bisazido(diphenylamino)borane [Ph2NB(N3)2] under matrix isolation condition. During sublimation an extremely dangerous and highly explosive triazidoborane [B(N3)3] was sublimed. Upon photolysis the corresponding photo product NNBN was identified. The BN derivative of o-benzyne is called 1,2-azaborine and 9,10-didehydro-9-aza-10-boraphenanthrene (E) is a higher analog of 1,2-azaborine. To obtain E, different routes have been followed: (i) thermolysis of azidoborane, (ii) thermolysis of silyl(silyloxy)aminoborole and (iii) base induced dehydrohalogenation. This research has produced a number of key findings: a new type of azidoborane is introduced and its cyclotrimerization due to high Lewis acidity is observed; formal dyotropic rearrangement of aminoborole to azaborine fragment is attained; dehydrohalogenation of appropriate aminoborane by suitable bases has been established.","Die Bor-Stickstoff-Derivate von organischen Molekülen sind aufgrund ihrer einzigartigen chemischen Eigenschaften von wissenschaftlichem Interesse. Die folgende Doktorarbeit beschäftigt sich mit Wegen zur Synthese von Diphenylaminoborylen und 9,10-Didehydro-9,10-azaboraphenanthren (E). Das Diphenylaminoborylen ist isostrukturell zum Vinyliden, das Didehydro-9-aza-10-boraphenanthren ist als Vertreter eines 1,2-Azaborins isostrukturell zu Didehydrobenzol (Arin) bzw. Phenanthren. Es war beabsichtigt, das Diphenylaminoborylen unter Matrixisolationsbedingungen aus Bisazido(diphenylamino)boran [Ph2NB(N3)2] darzustellen. Während der Sublimation entstand jedoch das gefährliche, hochexplosive Triazidoboran [B(N3)3]. Nach Photolyse wurde das entsprechende Photoprodukt NNBN identifiziert. Um E zu erhalten, wurden drei Syntheserouten untersucht: erstens die Thermolyse von 9-Azido-9-borafluoren, zweitens die Thermolyse von Silyl(silyloxy)aminoborol und drittens baseninduzierte Dehydrohalogenierung. Im Zuge der Doktorarbeit wurden mehrere wesentliche Erkenntnisse gewonnen: Eine neue Klasse von Azidoboranen wird vorgestellt und deren Cyclotrimerisierung durch hohe Lewis-Acidität wird beobachtet; die formale dyotrope Umlagerung von Aminoborol zu einem Azaborinfragment wurde realisiert und die Dehydrohalogenierung von geeigneten Aminoboranen durch passende Basen konnte etabliert werden."]},{"key":"dc:title","label":"Title","values":["Boron-Nitrogen Derivatives of Organic Reactive Intermediates"]}]}],"canonical_facts":{"dc:date.issued":["2012"],"dc:description.other":["The boron-nitrogen derivatives of organic molecules have attracted the chemists’ attention due to their distinct chemical properties. This dissertation focuses on ways to access the diphenylaminoborylene (Ph2NB:) and 9,10-didehydro-9-aza-10-boraphenanthrene (E). The diphenylaminoborylene, is isostructural to vinylidene and that was intended to generate from bisazido(diphenylamino)borane [Ph2NB(N3)2] under matrix isolation condition. During sublimation an extremely dangerous and highly explosive triazidoborane [B(N3)3] was sublimed. Upon photolysis the corresponding photo product NNBN was identified. The BN derivative of o-benzyne is called 1,2-azaborine and 9,10-didehydro-9-aza-10-boraphenanthrene (E) is a higher analog of 1,2-azaborine. To obtain E, different routes have been followed: (i) thermolysis of azidoborane, (ii) thermolysis of silyl(silyloxy)aminoborole and (iii) base induced dehydrohalogenation. This research has produced a number of key findings: a new type of azidoborane is introduced and its cyclotrimerization due to high Lewis acidity is observed; formal dyotropic rearrangement of aminoborole to azaborine fragment is attained; dehydrohalogenation of appropriate aminoborane by suitable bases has been established.","Die Bor-Stickstoff-Derivate von organischen Molekülen sind aufgrund ihrer einzigartigen chemischen Eigenschaften von wissenschaftlichem Interesse. Die folgende Doktorarbeit beschäftigt sich mit Wegen zur Synthese von Diphenylaminoborylen und 9,10-Didehydro-9,10-azaboraphenanthren (E). Das Diphenylaminoborylen ist isostrukturell zum Vinyliden, das Didehydro-9-aza-10-boraphenanthren ist als Vertreter eines 1,2-Azaborins isostrukturell zu Didehydrobenzol (Arin) bzw. Phenanthren. Es war beabsichtigt, das Diphenylaminoborylen unter Matrixisolationsbedingungen aus Bisazido(diphenylamino)boran [Ph2NB(N3)2] darzustellen. Während der Sublimation entstand jedoch das gefährliche, hochexplosive Triazidoboran [B(N3)3]. Nach Photolyse wurde das entsprechende Photoprodukt NNBN identifiziert. Um E zu erhalten, wurden drei Syntheserouten untersucht: erstens die Thermolyse von 9-Azido-9-borafluoren, zweitens die Thermolyse von Silyl(silyloxy)aminoborol und drittens baseninduzierte Dehydrohalogenierung. Im Zuge der Doktorarbeit wurden mehrere wesentliche Erkenntnisse gewonnen: Eine neue Klasse von Azidoboranen wird vorgestellt und deren Cyclotrimerisierung durch hohe Lewis-Acidität wird beobachtet; die formale dyotrope Umlagerung von Aminoborol zu einem Azaborinfragment wurde realisiert und die Dehydrohalogenierung von geeigneten Aminoboranen durch passende Basen konnte etabliert werden."],"dc:identifier":["hdl:10900/49632"],"dc:title":["Boron-Nitrogen Derivatives of Organic Reactive Intermediates"],"dc:type":["PhDThesis"]},"updated_at":"2026-08-21T22:21:56Z"}