E-H (E = B, Si, C) Bond activation by tuning structural and electronic properties of phosphenium cations
In this work, strategic enhancement of electrophilicity of phosphenium cations for the purpose of small-molecule activation was described. Our synthetic methodology for generation of novel two-coordinate phosphorus(III)-based compounds [{C6H4(MeN)2C}2C·PR]2+ ([2a]2+, R = NiPr2; [2b]2+, R = Ph) was b...
| Main Authors: | , , , |
|---|---|
| Other Authors: | |
| Format: | Journal Article |
| Language: | English |
| Published: |
2020
|
| Subjects: | |
| Online Access: | https://hdl.handle.net/10356/142688 |
| _version_ | 1826124153580683264 |
|---|---|
| author | Đorđević, Nemanja Ganguly, Rakesh Petković, Milena Vidović, Dragoslav |
| author2 | School of Physical and Mathematical Sciences |
| author_facet | School of Physical and Mathematical Sciences Đorđević, Nemanja Ganguly, Rakesh Petković, Milena Vidović, Dragoslav |
| author_sort | Đorđević, Nemanja |
| collection | NTU |
| description | In this work, strategic enhancement of electrophilicity of phosphenium cations for the purpose of small-molecule activation was described. Our synthetic methodology for generation of novel two-coordinate phosphorus(III)-based compounds [{C6H4(MeN)2C}2C·PR]2+ ([2a]2+, R = NiPr2; [2b]2+, R = Ph) was based on the exceptional electron-donating properties of the carbodicarbene ligand (CDC). The effects of P-centered substituent exchange and increase in the overall positive charge on small substrate activation were comparatively determined by incorporating the bis(amino)phosphenium ion [(iPr2N)2P]+ ([1]+) in this study. Implemented structural and electronic modifications of phosphenium salts were computationally verified and subsequently confirmed by isolation and characterization of the corresponding E-H (E = B, Si, C) bond activation products. While both phosphenium mono- and dications oxidatively inserted/cleaved the B-H bond of Lewis base stabilized boranes, the increased electrophilicity of doubly charged species also afforded the activation of significantly less hydridic Si-H and C-H bonds. The preference of [2a]2+ and [2b]2+ to abstract the hydride rather than to insert into the corresponding bond of silanes, as well as the formation of the carbodicarbene-stabilized parent phosphenium ion [{C6H4(MeN)2C}2C·PH2]+ ([2·PH2]+) were experimentally validated. |
| first_indexed | 2024-10-01T06:16:00Z |
| format | Journal Article |
| id | ntu-10356/142688 |
| institution | Nanyang Technological University |
| language | English |
| last_indexed | 2024-10-01T06:16:00Z |
| publishDate | 2020 |
| record_format | dspace |
| spelling | ntu-10356/1426882020-06-26T08:29:56Z E-H (E = B, Si, C) Bond activation by tuning structural and electronic properties of phosphenium cations Đorđević, Nemanja Ganguly, Rakesh Petković, Milena Vidović, Dragoslav School of Physical and Mathematical Sciences Science::Chemistry Hydrogen Abstraction Anions In this work, strategic enhancement of electrophilicity of phosphenium cations for the purpose of small-molecule activation was described. Our synthetic methodology for generation of novel two-coordinate phosphorus(III)-based compounds [{C6H4(MeN)2C}2C·PR]2+ ([2a]2+, R = NiPr2; [2b]2+, R = Ph) was based on the exceptional electron-donating properties of the carbodicarbene ligand (CDC). The effects of P-centered substituent exchange and increase in the overall positive charge on small substrate activation were comparatively determined by incorporating the bis(amino)phosphenium ion [(iPr2N)2P]+ ([1]+) in this study. Implemented structural and electronic modifications of phosphenium salts were computationally verified and subsequently confirmed by isolation and characterization of the corresponding E-H (E = B, Si, C) bond activation products. While both phosphenium mono- and dications oxidatively inserted/cleaved the B-H bond of Lewis base stabilized boranes, the increased electrophilicity of doubly charged species also afforded the activation of significantly less hydridic Si-H and C-H bonds. The preference of [2a]2+ and [2b]2+ to abstract the hydride rather than to insert into the corresponding bond of silanes, as well as the formation of the carbodicarbene-stabilized parent phosphenium ion [{C6H4(MeN)2C}2C·PH2]+ ([2·PH2]+) were experimentally validated. 2020-06-26T08:29:55Z 2020-06-26T08:29:55Z 2017 Journal Article Đorđević, N., Ganguly, R., Petković, M., & Vidović, D. (2017). E-H (E = B, Si, C) Bond activation by tuning structural and electronic properties of phosphenium cations. Inorganic chemistry, 56(23), 14671–14681. doi:10.1021/acs.inorgchem.7b02579 0020-1669 https://hdl.handle.net/10356/142688 10.1021/acs.inorgchem.7b02579 29161025 2-s2.0-85037605739 23 56 14671 14681 en Inorganic chemistry © 2017 American Chemical Society. All rights reserved. |
| spellingShingle | Science::Chemistry Hydrogen Abstraction Anions Đorđević, Nemanja Ganguly, Rakesh Petković, Milena Vidović, Dragoslav E-H (E = B, Si, C) Bond activation by tuning structural and electronic properties of phosphenium cations |
| title | E-H (E = B, Si, C) Bond activation by tuning structural and electronic properties of phosphenium cations |
| title_full | E-H (E = B, Si, C) Bond activation by tuning structural and electronic properties of phosphenium cations |
| title_fullStr | E-H (E = B, Si, C) Bond activation by tuning structural and electronic properties of phosphenium cations |
| title_full_unstemmed | E-H (E = B, Si, C) Bond activation by tuning structural and electronic properties of phosphenium cations |
| title_short | E-H (E = B, Si, C) Bond activation by tuning structural and electronic properties of phosphenium cations |
| title_sort | e h e b si c bond activation by tuning structural and electronic properties of phosphenium cations |
| topic | Science::Chemistry Hydrogen Abstraction Anions |
| url | https://hdl.handle.net/10356/142688 |
| work_keys_str_mv | AT đorđevicnemanja ehebsicbondactivationbytuningstructuralandelectronicpropertiesofphospheniumcations AT gangulyrakesh ehebsicbondactivationbytuningstructuralandelectronicpropertiesofphospheniumcations AT petkovicmilena ehebsicbondactivationbytuningstructuralandelectronicpropertiesofphospheniumcations AT vidovicdragoslav ehebsicbondactivationbytuningstructuralandelectronicpropertiesofphospheniumcations |