{"id":{"repo_id":"uiuc","oai_identifier":"oai:www.ideals.illinois.edu:2142/70434"},"canonical_url":"https://search.dev.ndltd.org/etd/uiuc/oai:www.ideals.illinois.edu:2142/70434","repository":{"repo_id":"uiuc","name":"University of Illinois - Urbana-Champaign","base_url":"https://www.ideals.illinois.edu/oai-pmh"},"display":{"title":"Photochemical Rearrangements of Tetraarylborate Salts: Direct Irradiation, Triplet Sensitization, and Single Electron Transfer","abstract":"The photochemistry of tetraarylborate salts has been investigated by direct irradiation, triplet sensitization and under single electron transfer conditions. Irradiation of sodium tetraphenylborate at 254 nm in either acetonitrile or THF produces 2,7,7-triphenyl-7-boratabicyclo (4.1.0) hepta-2,4-diene. The rearrangement was also observed to occur with other tetraarylborate salts. The mechanism which produces these novel boratanorcaradienes is similar to the well-known di-$\\pi$-methane rearrangement of 1,4-dienes. The &quot;di-$\\pi$-borate&quot; rearrangement has also been shown to occur under conditions of triplet sensitization. The boratanorcaradienes are oxygen- and water-sensitive compounds which possess many unique properties. Among these are a broad absorption in the visible region of the UV-vis spectrum, which gives rise to the observed color, and an extremely low oxidation potential. Interesting sigmatropic and electrocyclic rearrangements have also been recognized in these systems. Oxidation of tetraphenylborate by excited state electron acceptors results in decomposition of the borate and formation of biphenyl in quantitative yield.","abstract_html":"The photochemistry of tetraarylborate salts has been investigated by direct irradiation, triplet sensitization and under single electron transfer conditions. Irradiation of sodium tetraphenylborate at 254 nm in either acetonitrile or THF produces 2,7,7-triphenyl-7-boratabicyclo (4.1.0) hepta-2,4-diene. The rearrangement was also observed to occur with other tetraarylborate salts. The mechanism which produces these novel boratanorcaradienes is similar to the well-known di-<span class=\"etd-inline-math\">&pi;</span>-methane rearrangement of 1,4-dienes. The &amp;quot;di-<span class=\"etd-inline-math\">&pi;</span>-borate&amp;quot; rearrangement has also been shown to occur under conditions of triplet sensitization. The boratanorcaradienes are oxygen- and water-sensitive compounds which possess many unique properties. Among these are a broad absorption in the visible region of the UV-vis spectrum, which gives rise to the observed color, and an extremely low oxidation potential. Interesting sigmatropic and electrocyclic rearrangements have also been recognized in these systems. Oxidation of tetraphenylborate by excited state electron acceptors results in decomposition of the borate and formation of biphenyl in quantitative yield.","abstract_has_math":true,"creators":["Wilkey, John David"],"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":"2014-12-15T23:19:26Z","date_published":"2014-12-15T23:19:26Z","updated_at":"2026-07-22T22:26:02Z","subjects":["Chemistry, Organic"],"languages":[],"rights":[],"rights_urls":[],"identifier_entries":[{"key":"dc:identifier","label":"Identifier","values":["(UMI)AAI8908889"],"render_values":[{"text":"(UMI)AAI8908889","href":null,"code":true}]}]},"links":{"outbound_url":"http://hdl.handle.net/2142/70434","outbound_label":"Handle","outbound_source":"dc:identifier"},"metadata_groups":[{"id":"people","label":"People","entries":[{"key":"dc:creator","label":"Author","values":["Wilkey, John David"]}]},{"id":"academic_context","label":"Academic Context","entries":[{"key":"dc:date","label":"Dc Date","values":["2014-12-15T23:19:26Z","10000-01-01","1988"]},{"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":"identifiers","label":"Identifiers","entries":[{"key":"dc:identifier","label":"Identifier","values":["(UMI)AAI8908889","http://hdl.handle.net/2142/70434"]}]},{"id":"additional","label":"Additional Metadata","entries":[{"key":"dc:description","label":"Description","values":["The photochemistry of tetraarylborate salts has been investigated by direct irradiation, triplet sensitization and under single electron transfer conditions. Irradiation of sodium tetraphenylborate at 254 nm in either acetonitrile or THF produces 2,7,7-triphenyl-7-boratabicyclo (4.1.0) hepta-2,4-diene. The rearrangement was also observed to occur with other tetraarylborate salts. The mechanism which produces these novel boratanorcaradienes is similar to the well-known di-$\\pi$-methane rearrangement of 1,4-dienes. The &quot;di-$\\pi$-borate&quot; rearrangement has also been shown to occur under conditions of triplet sensitization. The boratanorcaradienes are oxygen- and water-sensitive compounds which possess many unique properties. Among these are a broad absorption in the visible region of the UV-vis spectrum, which gives rise to the observed color, and an extremely low oxidation potential. Interesting sigmatropic and electrocyclic rearrangements have also been recognized in these systems. Oxidation of tetraphenylborate by excited state electron acceptors results in decomposition of the borate and formation of biphenyl in quantitative yield.","Made available in DSpace on 2014-12-15T23:19:26Z (GMT). No. of bitstreams: 1 8908889.pdf: 4180805 bytes, checksum: 7762ff833805e98cbb227a5107f45ef2 (MD5) Previous issue date: 1988","Embargo set by: Seth Robbins for item 70600 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","132 p.","Thesis (Ph.D.)--University of Illinois at Urbana-Champaign, 1988."]},{"key":"dc:title","label":"Title","values":["Photochemical Rearrangements of Tetraarylborate Salts: Direct Irradiation, Triplet Sensitization, and Single Electron Transfer"]}]}],"canonical_facts":{"dc:creator":["Wilkey, John David"],"dc:date":["2014-12-15T23:19:26Z","10000-01-01","1988"],"dc:description":["The photochemistry of tetraarylborate salts has been investigated by direct irradiation, triplet sensitization and under single electron transfer conditions. Irradiation of sodium tetraphenylborate at 254 nm in either acetonitrile or THF produces 2,7,7-triphenyl-7-boratabicyclo (4.1.0) hepta-2,4-diene. The rearrangement was also observed to occur with other tetraarylborate salts. The mechanism which produces these novel boratanorcaradienes is similar to the well-known di-$\\pi$-methane rearrangement of 1,4-dienes. The &quot;di-$\\pi$-borate&quot; rearrangement has also been shown to occur under conditions of triplet sensitization. The boratanorcaradienes are oxygen- and water-sensitive compounds which possess many unique properties. Among these are a broad absorption in the visible region of the UV-vis spectrum, which gives rise to the observed color, and an extremely low oxidation potential. Interesting sigmatropic and electrocyclic rearrangements have also been recognized in these systems. Oxidation of tetraphenylborate by excited state electron acceptors results in decomposition of the borate and formation of biphenyl in quantitative yield.","Made available in DSpace on 2014-12-15T23:19:26Z (GMT). No. of bitstreams: 1 8908889.pdf: 4180805 bytes, checksum: 7762ff833805e98cbb227a5107f45ef2 (MD5) Previous issue date: 1988","Embargo set by: Seth Robbins for item 70600 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","132 p.","Thesis (Ph.D.)--University of Illinois at Urbana-Champaign, 1988."],"dc:identifier":["(UMI)AAI8908889","http://hdl.handle.net/2142/70434"],"dc:subject":["Chemistry, Organic"],"dc:title":["Photochemical Rearrangements of Tetraarylborate Salts: Direct Irradiation, Triplet Sensitization, and Single Electron Transfer"],"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":"2026-07-22T22:26:02Z"}