A crystalline diazadiborinine radical cation and its boron-centered radical reactivity
One‐electron oxidation of 1,4,2,5‐diazadiborinine 1 has been studied. While the reaction of 1 a bearing phenyl groups on the B atoms with AgAl{OC(CF3)3}4 afforded a complex mixture, the same oxidation reaction with 1 b featuring bulky mesityl substituents on the B atoms rendered the corresponding ca...
| Main Authors: | , , , , |
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| Other Authors: | |
| Format: | Journal Article |
| Language: | English |
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2020
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| Subjects: | |
| Online Access: | https://hdl.handle.net/10356/137708 |
| _version_ | 1826120808979759104 |
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| author | Wang, Baolin Li, Yongxin Ganguly, Rakesh Webster, Richard David Kinjo, Rei |
| author2 | School of Physical and Mathematical Sciences |
| author_facet | School of Physical and Mathematical Sciences Wang, Baolin Li, Yongxin Ganguly, Rakesh Webster, Richard David Kinjo, Rei |
| author_sort | Wang, Baolin |
| collection | NTU |
| description | One‐electron oxidation of 1,4,2,5‐diazadiborinine 1 has been studied. While the reaction of 1 a bearing phenyl groups on the B atoms with AgAl{OC(CF3)3}4 afforded a complex mixture, the same oxidation reaction with 1 b featuring bulky mesityl substituents on the B atoms rendered the corresponding cation radical 2 b as an isolable species. X‐ray diffraction analysis, EPR spectroscopy, and DFT calculations of 2 b revealed the delocalization of the unpaired electron over the entire π‐system of 2 b, as well as a large spin density (0.76 in total) on the two equivalent boron atoms. The chemical trapping reaction of 2 b with p‐benzoquinone and triphenyltin hydride afforded the dicationic species 3 containing two newly formed B−O bonds and the monocationic product 2b‐H containing a B−H bond, respectively, thus confirming the boron‐centered radical reactivity of 2 b. |
| first_indexed | 2024-10-01T05:22:31Z |
| format | Journal Article |
| id | ntu-10356/137708 |
| institution | Nanyang Technological University |
| language | English |
| last_indexed | 2024-10-01T05:22:31Z |
| publishDate | 2020 |
| record_format | dspace |
| spelling | ntu-10356/1377082020-04-09T04:39:35Z A crystalline diazadiborinine radical cation and its boron-centered radical reactivity Wang, Baolin Li, Yongxin Ganguly, Rakesh Webster, Richard David Kinjo, Rei School of Physical and Mathematical Sciences Science::Chemistry Boron B,N Heterocycles One‐electron oxidation of 1,4,2,5‐diazadiborinine 1 has been studied. While the reaction of 1 a bearing phenyl groups on the B atoms with AgAl{OC(CF3)3}4 afforded a complex mixture, the same oxidation reaction with 1 b featuring bulky mesityl substituents on the B atoms rendered the corresponding cation radical 2 b as an isolable species. X‐ray diffraction analysis, EPR spectroscopy, and DFT calculations of 2 b revealed the delocalization of the unpaired electron over the entire π‐system of 2 b, as well as a large spin density (0.76 in total) on the two equivalent boron atoms. The chemical trapping reaction of 2 b with p‐benzoquinone and triphenyltin hydride afforded the dicationic species 3 containing two newly formed B−O bonds and the monocationic product 2b‐H containing a B−H bond, respectively, thus confirming the boron‐centered radical reactivity of 2 b. MOE (Min. of Education, S’pore) 2020-04-09T04:39:35Z 2020-04-09T04:39:35Z 2018 Journal Article Wang, B., Li, Y., Ganguly, R., Webster, R. D., & Kinjo, R. (2018). A crystalline diazadiborinine radical cation and its boron-centered radical reactivity. Angewandte Chemie International Edition, 57(26), 7826-7829. doi:10.1002/anie.201803547 1433-7851 https://hdl.handle.net/10356/137708 10.1002/anie.201803547 29683242 2-s2.0-85048834267 26 57 7826 7829 en Angewandte Chemie International Edition © 2018 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim. All rights reserved. |
| spellingShingle | Science::Chemistry Boron B,N Heterocycles Wang, Baolin Li, Yongxin Ganguly, Rakesh Webster, Richard David Kinjo, Rei A crystalline diazadiborinine radical cation and its boron-centered radical reactivity |
| title | A crystalline diazadiborinine radical cation and its boron-centered radical reactivity |
| title_full | A crystalline diazadiborinine radical cation and its boron-centered radical reactivity |
| title_fullStr | A crystalline diazadiborinine radical cation and its boron-centered radical reactivity |
| title_full_unstemmed | A crystalline diazadiborinine radical cation and its boron-centered radical reactivity |
| title_short | A crystalline diazadiborinine radical cation and its boron-centered radical reactivity |
| title_sort | crystalline diazadiborinine radical cation and its boron centered radical reactivity |
| topic | Science::Chemistry Boron B,N Heterocycles |
| url | https://hdl.handle.net/10356/137708 |
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