Building a lewis acidic phosphorus
This work involves the synthesis and characterization of phosphenium cations whose stability reflects the σ- and π- donating properties of carbone ligands. A coordinatively unsaturated P(III)-containing dication, [iPr2NPC(PPh3)2]2+, has been synthesized and fully characterized by single crystal X-ra...
| Main Author: | |
|---|---|
| Other Authors: | |
| Format: | Thesis |
| Language: | English |
| Published: |
2016
|
| Subjects: | |
| Online Access: | https://hdl.handle.net/10356/66010 |
| _version_ | 1826126307262464000 |
|---|---|
| author | Tay, Madelyn Qin Yi |
| author2 | Dragoslav Vidovic |
| author_facet | Dragoslav Vidovic Tay, Madelyn Qin Yi |
| author_sort | Tay, Madelyn Qin Yi |
| collection | NTU |
| description | This work involves the synthesis and characterization of phosphenium cations whose stability reflects the σ- and π- donating properties of carbone ligands. A coordinatively unsaturated P(III)-containing dication, [iPr2NPC(PPh3)2]2+, has been synthesized and fully characterized by single crystal X-ray diffraction and theoretical calculations. Its reactivity towards DMAP, PMe3, H2O, MeOH, and CoCp2 is presented; no reactions were observed with 2-butyne, dimethylbutadiene and anisole. Two other putative Ph- and Cl-substituted dications [XPC(PPh3)2]2+ were targeted. These could not be observed directly, but evidence for their formation has been obtained through trapping with alkynes and 1,3-dienes to form dicationic species containing phosphirene and phospholene rings, respectively. Reduction of [Me2C2PClC(PPh3)2]2+ with elemental magnesium resulted in the formation of [Me2C2PC(PPh3)2]+, while the dehydrohalogenation of [Me2C4H4PClC(PPh3)2]2+ by 2-methylpyridine resulted in the formation of a phosphole. Preliminary studies on the hydrolysis of the Cl-substituted phosphirenium salt, [Me2C2PClC(PPh3)2]2+ shows a possible formation of a stable phosphirene oxide. |
| first_indexed | 2024-10-01T06:50:33Z |
| format | Thesis |
| id | ntu-10356/66010 |
| institution | Nanyang Technological University |
| language | English |
| last_indexed | 2024-10-01T06:50:33Z |
| publishDate | 2016 |
| record_format | dspace |
| spelling | ntu-10356/660102023-02-28T23:51:48Z Building a lewis acidic phosphorus Tay, Madelyn Qin Yi Dragoslav Vidovic School of Physical and Mathematical Sciences DRNTU::Science::Chemistry::Organic chemistry::Organometallic compounds This work involves the synthesis and characterization of phosphenium cations whose stability reflects the σ- and π- donating properties of carbone ligands. A coordinatively unsaturated P(III)-containing dication, [iPr2NPC(PPh3)2]2+, has been synthesized and fully characterized by single crystal X-ray diffraction and theoretical calculations. Its reactivity towards DMAP, PMe3, H2O, MeOH, and CoCp2 is presented; no reactions were observed with 2-butyne, dimethylbutadiene and anisole. Two other putative Ph- and Cl-substituted dications [XPC(PPh3)2]2+ were targeted. These could not be observed directly, but evidence for their formation has been obtained through trapping with alkynes and 1,3-dienes to form dicationic species containing phosphirene and phospholene rings, respectively. Reduction of [Me2C2PClC(PPh3)2]2+ with elemental magnesium resulted in the formation of [Me2C2PC(PPh3)2]+, while the dehydrohalogenation of [Me2C4H4PClC(PPh3)2]2+ by 2-methylpyridine resulted in the formation of a phosphole. Preliminary studies on the hydrolysis of the Cl-substituted phosphirenium salt, [Me2C2PClC(PPh3)2]2+ shows a possible formation of a stable phosphirene oxide. CHEMISTRY and BIOLOGICAL CHEMISTRY 2016-02-29T02:05:41Z 2016-02-29T02:05:41Z 2016 Thesis Tay, M. Q. Y. (2016). Building a lewis acidic phosphorus. Doctoral thesis, Nanyang Technological University, Singapore. https://hdl.handle.net/10356/66010 10.32657/10356/66010 en 184 p. application/pdf |
| spellingShingle | DRNTU::Science::Chemistry::Organic chemistry::Organometallic compounds Tay, Madelyn Qin Yi Building a lewis acidic phosphorus |
| title | Building a lewis acidic phosphorus |
| title_full | Building a lewis acidic phosphorus |
| title_fullStr | Building a lewis acidic phosphorus |
| title_full_unstemmed | Building a lewis acidic phosphorus |
| title_short | Building a lewis acidic phosphorus |
| title_sort | building a lewis acidic phosphorus |
| topic | DRNTU::Science::Chemistry::Organic chemistry::Organometallic compounds |
| url | https://hdl.handle.net/10356/66010 |
| work_keys_str_mv | AT taymadelynqinyi buildingalewisacidicphosphorus |