Molecules containing lewis acidic phosphorus - sites

Carbones (CL2) are a group of ligands with a divalent carbon(0) center. Due to the two available electron-pairs, carbones are considered to be substantially basic, which allowed them to serve as stabilizing ligands for a variety of the highly labile species. In this work, we report the synthesis of...

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Main Author: Ilic, Gordana
Other Authors: Kinjo Rei
Format: Theses and Dissertations
Language:English
Published: 2018
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Online Access:http://hdl.handle.net/10356/73215
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Institution: Nanyang Technological University
Language: English
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spelling sg-ntu-dr.10356-732152023-02-28T23:32:50Z Molecules containing lewis acidic phosphorus - sites Ilic, Gordana Kinjo Rei School of Physical and Mathematical Sciences DRNTU::Science::Chemistry::Inorganic chemistry::Non-metals Carbones (CL2) are a group of ligands with a divalent carbon(0) center. Due to the two available electron-pairs, carbones are considered to be substantially basic, which allowed them to serve as stabilizing ligands for a variety of the highly labile species. In this work, we report the synthesis of [(Ph3P)2CPNiPr2]2+, its two additional analogues [((RPh2P)2C)P(NR′2)]2+ (R = Ph, R′ = Cy; R = 1/2 (CH2)3, R′ = iPr;), and we explore its viability in the presence of various counterions. In addition, the oxophilic nature of [(Ph3P)2CPNiPr2]2+ is further studied in reactions with pyridine N-oxide (PyO). Surprisingly the resulting oxophosphonium dication proved to be an intermediate for the subsequent Baeyer-Villiger (BV)-resembling oxidation reaction, which proceeds through a Criegee intermediate to finally yield a rare P-C bond activation under mild conditions. Apart from being the first example of a PyO-driven BV oxidation, it is a safer alternative to the formerly used highly reactive mchlorobenzoic acid and hydrogen-peroxide. These results inspired us to also develop a route to the elusive parent-metaphosphonate species. This thesis also covers the synthetic pathway and the reactivity of the first carbone-stabilized parentmetaphosphonate [(Ph3P)2CP(O)2H]. ​Doctor of Philosophy (SPMS) 2018-01-23T01:24:10Z 2018-01-23T01:24:10Z 2018 Thesis Ilic, G. (2018). Molecules containing lewis acidic phosphorus - sites. Doctoral thesis, Nanyang Technological University, Singapore. http://hdl.handle.net/10356/73215 10.32657/10356/73215 en 204 p. application/pdf
institution Nanyang Technological University
building NTU Library
continent Asia
country Singapore
Singapore
content_provider NTU Library
collection DR-NTU
language English
topic DRNTU::Science::Chemistry::Inorganic chemistry::Non-metals
spellingShingle DRNTU::Science::Chemistry::Inorganic chemistry::Non-metals
Ilic, Gordana
Molecules containing lewis acidic phosphorus - sites
description Carbones (CL2) are a group of ligands with a divalent carbon(0) center. Due to the two available electron-pairs, carbones are considered to be substantially basic, which allowed them to serve as stabilizing ligands for a variety of the highly labile species. In this work, we report the synthesis of [(Ph3P)2CPNiPr2]2+, its two additional analogues [((RPh2P)2C)P(NR′2)]2+ (R = Ph, R′ = Cy; R = 1/2 (CH2)3, R′ = iPr;), and we explore its viability in the presence of various counterions. In addition, the oxophilic nature of [(Ph3P)2CPNiPr2]2+ is further studied in reactions with pyridine N-oxide (PyO). Surprisingly the resulting oxophosphonium dication proved to be an intermediate for the subsequent Baeyer-Villiger (BV)-resembling oxidation reaction, which proceeds through a Criegee intermediate to finally yield a rare P-C bond activation under mild conditions. Apart from being the first example of a PyO-driven BV oxidation, it is a safer alternative to the formerly used highly reactive mchlorobenzoic acid and hydrogen-peroxide. These results inspired us to also develop a route to the elusive parent-metaphosphonate species. This thesis also covers the synthetic pathway and the reactivity of the first carbone-stabilized parentmetaphosphonate [(Ph3P)2CP(O)2H].
author2 Kinjo Rei
author_facet Kinjo Rei
Ilic, Gordana
format Theses and Dissertations
author Ilic, Gordana
author_sort Ilic, Gordana
title Molecules containing lewis acidic phosphorus - sites
title_short Molecules containing lewis acidic phosphorus - sites
title_full Molecules containing lewis acidic phosphorus - sites
title_fullStr Molecules containing lewis acidic phosphorus - sites
title_full_unstemmed Molecules containing lewis acidic phosphorus - sites
title_sort molecules containing lewis acidic phosphorus - sites
publishDate 2018
url http://hdl.handle.net/10356/73215
_version_ 1759853240486199296