Synthesis of unique phosphazane macrocycles via steric activation of C-N bonds
Herein we describe that oxidation reactions of the dimeric cyclophosphazanes, [{P(μ-NR)}2(μ-NR)]2, R = tBu (1), to produce a series of diagonally dioxidized products P4(μ-N tBu)6E2 [E = O (2), S (3), and Se (4)] and tetraoxidized frameworks. The latter display an unexpected C-N bond activation and c...
| Main Authors: | , , , , , , , , , |
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| Format: | Journal Article |
| Language: | English |
| Published: |
2020
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| Online Access: | https://hdl.handle.net/10356/140059 |
| _version_ | 1811689777027612672 |
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| author | Shi, Xiaoyan Martin, Katherine Ann Liang, Rong Zheng Star, Daniel G. Li, Yongxin Ganguly, Rakesh Sim, Ying Tan, Davin Díaz, Jesús García, Felipe |
| author2 | School of Physical and Mathematical Sciences |
| author_facet | School of Physical and Mathematical Sciences Shi, Xiaoyan Martin, Katherine Ann Liang, Rong Zheng Star, Daniel G. Li, Yongxin Ganguly, Rakesh Sim, Ying Tan, Davin Díaz, Jesús García, Felipe |
| author_sort | Shi, Xiaoyan |
| collection | NTU |
| description | Herein we describe that oxidation reactions of the dimeric cyclophosphazanes, [{P(μ-NR)}2(μ-NR)]2, R = tBu (1), to produce a series of diagonally dioxidized products P4(μ-N tBu)6E2 [E = O (2), S (3), and Se (4)] and tetraoxidized frameworks. The latter display an unexpected C-N bond activation and cleavage to produce a series of novel phosphazane macrocyclic arrangements containing newly formed N-H bonds. Macromolecules P4(μ-N tBu)4(μ-NH)2O4 (5) and P4(μ-N tBu)3(μ-NH)3E4, E = S (6) and Se (7), dicleaved and tricleaved products, respectively, are rare examples of dimeric macrocycles containing NH bridging groups. Our theoretical and experimental studies illustrate that the extent to which these C-N bonds are cleaved can be controlled by modification of steric parameters in their synthesis, by adjusting either the steric bulk of the substituents in the parent framework or the size of the chalcogen element introduced during the oxidation process. Our findings represent new synthetic pathways for the synthesis of otherwise-elusive macrocycle arrangements within the phosphazane family. |
| first_indexed | 2024-10-01T05:53:29Z |
| format | Journal Article |
| id | ntu-10356/140059 |
| institution | Nanyang Technological University |
| language | English |
| last_indexed | 2024-10-01T05:53:29Z |
| publishDate | 2020 |
| record_format | dspace |
| spelling | ntu-10356/1400592020-05-26T06:04:59Z Synthesis of unique phosphazane macrocycles via steric activation of C-N bonds Shi, Xiaoyan Martin, Katherine Ann Liang, Rong Zheng Star, Daniel G. Li, Yongxin Ganguly, Rakesh Sim, Ying Tan, Davin Díaz, Jesús García, Felipe School of Physical and Mathematical Sciences Science::Chemistry Group 16 Compounds Bond Cleavage Herein we describe that oxidation reactions of the dimeric cyclophosphazanes, [{P(μ-NR)}2(μ-NR)]2, R = tBu (1), to produce a series of diagonally dioxidized products P4(μ-N tBu)6E2 [E = O (2), S (3), and Se (4)] and tetraoxidized frameworks. The latter display an unexpected C-N bond activation and cleavage to produce a series of novel phosphazane macrocyclic arrangements containing newly formed N-H bonds. Macromolecules P4(μ-N tBu)4(μ-NH)2O4 (5) and P4(μ-N tBu)3(μ-NH)3E4, E = S (6) and Se (7), dicleaved and tricleaved products, respectively, are rare examples of dimeric macrocycles containing NH bridging groups. Our theoretical and experimental studies illustrate that the extent to which these C-N bonds are cleaved can be controlled by modification of steric parameters in their synthesis, by adjusting either the steric bulk of the substituents in the parent framework or the size of the chalcogen element introduced during the oxidation process. Our findings represent new synthetic pathways for the synthesis of otherwise-elusive macrocycle arrangements within the phosphazane family. ASTAR (Agency for Sci., Tech. and Research, S’pore) MOE (Min. of Education, S’pore) 2020-05-26T06:04:59Z 2020-05-26T06:04:59Z 2018 Journal Article Shi, Y. X., Martin, K. A., Liang, R. Z., Star, D. G., Li, Y., Ganguly, R., . . . García, F. (2018). Synthesis of unique phosphazane macrocycles via steric activation of C-N bonds. Inorganic Chemistry, 57(17), 10993-11004. doi:10.1021/acs.inorgchem.8b01596 0020-1669 https://hdl.handle.net/10356/140059 10.1021/acs.inorgchem.8b01596 30125095 2-s2.0-85053041596 17 57 10993 11004 en Inorganic Chemistry © 2018 American Chemical Society. All rights reserved. |
| spellingShingle | Science::Chemistry Group 16 Compounds Bond Cleavage Shi, Xiaoyan Martin, Katherine Ann Liang, Rong Zheng Star, Daniel G. Li, Yongxin Ganguly, Rakesh Sim, Ying Tan, Davin Díaz, Jesús García, Felipe Synthesis of unique phosphazane macrocycles via steric activation of C-N bonds |
| title | Synthesis of unique phosphazane macrocycles via steric activation of C-N bonds |
| title_full | Synthesis of unique phosphazane macrocycles via steric activation of C-N bonds |
| title_fullStr | Synthesis of unique phosphazane macrocycles via steric activation of C-N bonds |
| title_full_unstemmed | Synthesis of unique phosphazane macrocycles via steric activation of C-N bonds |
| title_short | Synthesis of unique phosphazane macrocycles via steric activation of C-N bonds |
| title_sort | synthesis of unique phosphazane macrocycles via steric activation of c n bonds |
| topic | Science::Chemistry Group 16 Compounds Bond Cleavage |
| url | https://hdl.handle.net/10356/140059 |
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