{"title":"激发态三(五氟苯基)硼烷作为强单电子氧化剂:光物理性质和催化","authors":"Yoshitaka Aramaki, Yuki Uchida, Ryo Ishikawa, Takashi Ooi","doi":"10.1016/j.jpap.2023.100206","DOIUrl":null,"url":null,"abstract":"<div><p>The photophysical properties and photocatalysis of tris(pentafluorophenyl)borane [B(C<sub>6</sub>F<sub>5</sub>)<sub>3</sub>], known as a strong Lewis acid, were revealed. The excited-state B(C<sub>6</sub>F<sub>5</sub>)<sub>3</sub> exerts single-electron oxidation capability with an oxidation potential (<em>E</em><sub>red</sub>* = 2.02 V vs SCE) close to those of electronically unbiased toluene derivatives (<em>E</em><sub>ox</sub> = 2.01 to 2.29 V). This property was experimentally proven by the direct observation of the radical cation of the toluene dimer by the transient absorption spectroscopy of a mixture of B(C<sub>6</sub>F<sub>5</sub>)<sub>3</sub> and toluene. In cooperation with a suitable Brønsted base catalyst, B(C<sub>6</sub>F<sub>5</sub>)<sub>3</sub> catalytically generated benzylic radicals from toluene derivatives under photoirradiation for subsequent carbon-carbon bond-forming reactions.</p></div>","PeriodicalId":375,"journal":{"name":"Journal of Photochemistry and Photobiology","volume":"18 ","pages":"Article 100206"},"PeriodicalIF":3.2610,"publicationDate":"2023-08-29","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"https://www.sciencedirect.com/science/article/pii/S2666469023000477/pdfft?md5=1018f8b2d2ddae786dbd516b8204cade&pid=1-s2.0-S2666469023000477-main.pdf","citationCount":"0","resultStr":"{\"title\":\"Excited-state tris(pentafluorophenyl)borane as a strong single-electron oxidant: Photophysical properties and catalysis\",\"authors\":\"Yoshitaka Aramaki, Yuki Uchida, Ryo Ishikawa, Takashi Ooi\",\"doi\":\"10.1016/j.jpap.2023.100206\",\"DOIUrl\":null,\"url\":null,\"abstract\":\"<div><p>The photophysical properties and photocatalysis of tris(pentafluorophenyl)borane [B(C<sub>6</sub>F<sub>5</sub>)<sub>3</sub>], known as a strong Lewis acid, were revealed. The excited-state B(C<sub>6</sub>F<sub>5</sub>)<sub>3</sub> exerts single-electron oxidation capability with an oxidation potential (<em>E</em><sub>red</sub>* = 2.02 V vs SCE) close to those of electronically unbiased toluene derivatives (<em>E</em><sub>ox</sub> = 2.01 to 2.29 V). This property was experimentally proven by the direct observation of the radical cation of the toluene dimer by the transient absorption spectroscopy of a mixture of B(C<sub>6</sub>F<sub>5</sub>)<sub>3</sub> and toluene. In cooperation with a suitable Brønsted base catalyst, B(C<sub>6</sub>F<sub>5</sub>)<sub>3</sub> catalytically generated benzylic radicals from toluene derivatives under photoirradiation for subsequent carbon-carbon bond-forming reactions.</p></div>\",\"PeriodicalId\":375,\"journal\":{\"name\":\"Journal of Photochemistry and Photobiology\",\"volume\":\"18 \",\"pages\":\"Article 100206\"},\"PeriodicalIF\":3.2610,\"publicationDate\":\"2023-08-29\",\"publicationTypes\":\"Journal Article\",\"fieldsOfStudy\":null,\"isOpenAccess\":false,\"openAccessPdf\":\"https://www.sciencedirect.com/science/article/pii/S2666469023000477/pdfft?md5=1018f8b2d2ddae786dbd516b8204cade&pid=1-s2.0-S2666469023000477-main.pdf\",\"citationCount\":\"0\",\"resultStr\":null,\"platform\":\"Semanticscholar\",\"paperid\":null,\"PeriodicalName\":\"Journal of Photochemistry and Photobiology\",\"FirstCategoryId\":\"2\",\"ListUrlMain\":\"https://www.sciencedirect.com/science/article/pii/S2666469023000477\",\"RegionNum\":0,\"RegionCategory\":null,\"ArticlePicture\":[],\"TitleCN\":null,\"AbstractTextCN\":null,\"PMCID\":null,\"EPubDate\":\"\",\"PubModel\":\"\",\"JCR\":\"\",\"JCRName\":\"\",\"Score\":null,\"Total\":0}","platform":"Semanticscholar","paperid":null,"PeriodicalName":"Journal of Photochemistry and Photobiology","FirstCategoryId":"2","ListUrlMain":"https://www.sciencedirect.com/science/article/pii/S2666469023000477","RegionNum":0,"RegionCategory":null,"ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":null,"EPubDate":"","PubModel":"","JCR":"","JCRName":"","Score":null,"Total":0}
引用次数: 0
摘要
研究了强路易斯酸三(五氟苯基)硼烷[B(C6F5)3]的光物理性质和光催化作用。激发态B(C6F5)3具有单电子氧化能力，其氧化电位(Ered* = 2.02 V vs SCE)接近电子无偏甲苯衍生物的氧化电位(Eox = 2.01 ~ 2.29 V)。通过对B(C6F5)3和甲苯混合物的瞬态吸收光谱直接观察甲苯二聚体的自由基阳离子，实验证明了这一特性。在合适的Brønsted碱催化剂的作用下，B(C6F5)3在光照射下催化甲苯衍生物生成了苯自由基，用于随后的碳-碳成键反应。
Excited-state tris(pentafluorophenyl)borane as a strong single-electron oxidant: Photophysical properties and catalysis
The photophysical properties and photocatalysis of tris(pentafluorophenyl)borane [B(C6F5)3], known as a strong Lewis acid, were revealed. The excited-state B(C6F5)3 exerts single-electron oxidation capability with an oxidation potential (Ered* = 2.02 V vs SCE) close to those of electronically unbiased toluene derivatives (Eox = 2.01 to 2.29 V). This property was experimentally proven by the direct observation of the radical cation of the toluene dimer by the transient absorption spectroscopy of a mixture of B(C6F5)3 and toluene. In cooperation with a suitable Brønsted base catalyst, B(C6F5)3 catalytically generated benzylic radicals from toluene derivatives under photoirradiation for subsequent carbon-carbon bond-forming reactions.
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