An acid-free anionic oxoborane isoelectronic with carbonyl: facile access and transfer of a terminal B═O double bond
We disclose the synthesis and structural characterization of the first acid-free anionic oxoborane, [K(2.2.2-crypt)][(HCDippN)2BO] (1) (Dipp = 2,6- iPr2C6H3), which is isoelectronic with classical carbonyl compounds. 1 can readily be accessed from its borinic acid by a simple deprotonation/sequestra...
| Principais autores: | , , , , , |
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| Formato: | Journal article |
| Idioma: | English |
| Publicado em: |
American Chemical Society
2019
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| _version_ | 1826277034778689536 |
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| author | Loh, YK Porteous, K Fuentes, MÁ Do, D Hicks, J Aldridge, S |
| author_facet | Loh, YK Porteous, K Fuentes, MÁ Do, D Hicks, J Aldridge, S |
| author_sort | Loh, YK |
| collection | OXFORD |
| description | We disclose the synthesis and structural characterization of the first acid-free anionic oxoborane, [K(2.2.2-crypt)][(HCDippN)2BO] (1) (Dipp = 2,6- iPr2C6H3), which is isoelectronic with classical carbonyl compounds. 1 can readily be accessed from its borinic acid by a simple deprotonation/sequestration sequence. Crystallographic and density functional theory (DFT) analyses support the presence of a polarized terminal B═O double bond. Subsequent π bond metathesis converts the B═O bond to a heavier B═S containing system, affording the first anionic thioxoborane [K(2.2.2-crypt)][(HCDippN)2BS] (2), isoelectronic with thiocarbonyls. Facile B═O bond cleavage can also be achieved to access B-H and B-Cl bonds and, via a remarkable oxide (O2-) ion abstraction, to generate a borenium cation [(HCDippN)2B(NC5H5)][OTf] (4). By extension, 1 can act as an oxide transfer agent to organic substrates, a synthetic role traditionally associated with transition-metal compounds. Hence we show that B-O linkages, which are often considered to be thermodynamic sinks, can be activated under mild conditions toward bond cleavage and transfer, by exploiting the higher reactivity inherent in the B═O double bond. |
| first_indexed | 2024-03-06T23:22:49Z |
| format | Journal article |
| id | oxford-uuid:6955349f-92c8-4b3c-bb7f-bdc91596f780 |
| institution | University of Oxford |
| language | English |
| last_indexed | 2024-03-06T23:22:49Z |
| publishDate | 2019 |
| publisher | American Chemical Society |
| record_format | dspace |
| spelling | oxford-uuid:6955349f-92c8-4b3c-bb7f-bdc91596f7802022-03-26T18:50:35ZAn acid-free anionic oxoborane isoelectronic with carbonyl: facile access and transfer of a terminal B═O double bondJournal articlehttp://purl.org/coar/resource_type/c_dcae04bcuuid:6955349f-92c8-4b3c-bb7f-bdc91596f780EnglishSymplectic Elements at OxfordAmerican Chemical Society2019Loh, YKPorteous, KFuentes, MÁDo, DHicks, JAldridge, SWe disclose the synthesis and structural characterization of the first acid-free anionic oxoborane, [K(2.2.2-crypt)][(HCDippN)2BO] (1) (Dipp = 2,6- iPr2C6H3), which is isoelectronic with classical carbonyl compounds. 1 can readily be accessed from its borinic acid by a simple deprotonation/sequestration sequence. Crystallographic and density functional theory (DFT) analyses support the presence of a polarized terminal B═O double bond. Subsequent π bond metathesis converts the B═O bond to a heavier B═S containing system, affording the first anionic thioxoborane [K(2.2.2-crypt)][(HCDippN)2BS] (2), isoelectronic with thiocarbonyls. Facile B═O bond cleavage can also be achieved to access B-H and B-Cl bonds and, via a remarkable oxide (O2-) ion abstraction, to generate a borenium cation [(HCDippN)2B(NC5H5)][OTf] (4). By extension, 1 can act as an oxide transfer agent to organic substrates, a synthetic role traditionally associated with transition-metal compounds. Hence we show that B-O linkages, which are often considered to be thermodynamic sinks, can be activated under mild conditions toward bond cleavage and transfer, by exploiting the higher reactivity inherent in the B═O double bond. |
| spellingShingle | Loh, YK Porteous, K Fuentes, MÁ Do, D Hicks, J Aldridge, S An acid-free anionic oxoborane isoelectronic with carbonyl: facile access and transfer of a terminal B═O double bond |
| title | An acid-free anionic oxoborane isoelectronic with carbonyl: facile access and transfer of a terminal B═O double bond |
| title_full | An acid-free anionic oxoborane isoelectronic with carbonyl: facile access and transfer of a terminal B═O double bond |
| title_fullStr | An acid-free anionic oxoborane isoelectronic with carbonyl: facile access and transfer of a terminal B═O double bond |
| title_full_unstemmed | An acid-free anionic oxoborane isoelectronic with carbonyl: facile access and transfer of a terminal B═O double bond |
| title_short | An acid-free anionic oxoborane isoelectronic with carbonyl: facile access and transfer of a terminal B═O double bond |
| title_sort | acid free anionic oxoborane isoelectronic with carbonyl facile access and transfer of a terminal b═o double bond |
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