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Title: Synthesis and reactivity of 2-phosphaethynolate anion and phosphinecarboxamide
Author: Jupp, Andrew Robert
ISNI:       0000 0004 6495 8357
Awarding Body: University of Oxford
Current Institution: University of Oxford
Date of Award: 2016
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This thesis describes a novel synthesis of the 2-phosphaethynolate anion, [PCO]⁻, via reaction of the [P7]³⁻ Zintl cluster with carbon monoxide. The ligand properties of this fundamental molecule have been probed and compared to common isoelectronic pseudohalides: cyanate and isocyanate. The first ambient-temperature synthesis of the heavier congener, [PCS]⁻, is also reported, and studies show that this anion can act as an ambidentate ligand. The cycloaddition chemistry of [PCO]⁻ with heteroallenes afforded a range of novel anionic phosphorus-containing heterocycles. A collaborative study has shown that [PCO]⁻ can act as a catalyst for the trimerisation of isocyanates, and potential intermediates in this catalytic cycle have been isolated. By analogy with Wöhler's historic synthesis of urea, the reaction of [PCO]⁻ with ammonium salts yields phosphinecarboxamide. This unprecedented molecule is a rare example of an air-stable "user-friendly" primary phosphine, and its structure and ability to coordinate to metal centres were explored. It was found that this species has similar s donor and p acceptor properties to phosphine, PH3. This reactivity has been extended to incorporate N-functionalised phosphinecarboxamides with a range of different functional groups. The Brønsted acidity, P-functionalisation and oxidation chemistry of these species was subsequently investigated to afford a diverse family of carbamoyl-bearing phosphides, phosphines and phosphine oxides. Some of these species have great potential to become industrially relevant molecules in the future. Preliminary results showing the generality of the reaction of [PCO]⁻ with other protic nucleophiles are additionally presented.
Supervisor: Goicoechea, Jose Sponsor: Engineering and Physical Sciences Research Council
Qualification Name: Thesis (Ph.D.) Qualification Level: Doctoral
EThOS ID:  DOI: Not available