Synthesis and Complexation of a Bulky Silyl Phosphanide and Extended PNNNP Carbazole-based Ligand

In this work, the synthesis of the bulky phosphanide, [(iPr3Si)2P−] was investigated and optimised, leading to the isolation of the sodium phosphanide X2.14. This ligand was explored in preliminary coordinations with Co2+, Fe2+ and Zn2+ resulting in dimeric (X2.21, Co2+) and monomeric (X2.22, Fe2+ a...

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Main Author: Churchill, Olivia
Format: Thesis (University of Nottingham only)
Language:English
Published: 2024
Subjects:
Online Access:https://eprints.nottingham.ac.uk/77946/
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author Churchill, Olivia
author_facet Churchill, Olivia
author_sort Churchill, Olivia
building Nottingham Research Data Repository
collection Online Access
description In this work, the synthesis of the bulky phosphanide, [(iPr3Si)2P−] was investigated and optimised, leading to the isolation of the sodium phosphanide X2.14. This ligand was explored in preliminary coordinations with Co2+, Fe2+ and Zn2+ resulting in dimeric (X2.21, Co2+) and monomeric (X2.22, Fe2+ and X2.23, Zn2+) products respectively characterised by X-ray crystallography. A novel (PNNNP) pentadentate carbazole based ligand with nitrogen and phosphorus donors in close proximity was designed and retrosynthetically analysed. Pre-ligand X3.66 was successfully isolated and characterised with X-ray crystallography, 1H NMR, 31P{1H} NMR, IR, UV-vis spectroscopy and elemental analysis. Reduction of X3.66 (monoanionic) led to the isolation of another pre-ligand, X3.54 (trianionic) which was characterised by X-ray crystallography, 1H NMR, 13C{1H} NMR, 31P{1H} NMR, IR and UV-vis spectroscopy. Deprotonation of X3.66 was investigated. Direct addition of X3.66 to metal precursors, Fe2+, Cu+, Ni2+ and Zn2+ led to the isolation of complexes X4.23 (PNNNP, Ni2+), X4.24 (NNNP, Fe2+), X2.25 (PNNNP, Fe2+) X4.26 (ONNNO, Fe2+), X4.27 (PP, Cu+) and X4.29 (NNNP, Zn2+), which were all characterised by X-ray crystallography.
first_indexed 2025-11-14T21:01:07Z
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institution University of Nottingham Malaysia Campus
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language English
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publishDate 2024
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spelling nottingham-779462025-02-28T15:20:37Z https://eprints.nottingham.ac.uk/77946/ Synthesis and Complexation of a Bulky Silyl Phosphanide and Extended PNNNP Carbazole-based Ligand Churchill, Olivia In this work, the synthesis of the bulky phosphanide, [(iPr3Si)2P−] was investigated and optimised, leading to the isolation of the sodium phosphanide X2.14. This ligand was explored in preliminary coordinations with Co2+, Fe2+ and Zn2+ resulting in dimeric (X2.21, Co2+) and monomeric (X2.22, Fe2+ and X2.23, Zn2+) products respectively characterised by X-ray crystallography. A novel (PNNNP) pentadentate carbazole based ligand with nitrogen and phosphorus donors in close proximity was designed and retrosynthetically analysed. Pre-ligand X3.66 was successfully isolated and characterised with X-ray crystallography, 1H NMR, 31P{1H} NMR, IR, UV-vis spectroscopy and elemental analysis. Reduction of X3.66 (monoanionic) led to the isolation of another pre-ligand, X3.54 (trianionic) which was characterised by X-ray crystallography, 1H NMR, 13C{1H} NMR, 31P{1H} NMR, IR and UV-vis spectroscopy. Deprotonation of X3.66 was investigated. Direct addition of X3.66 to metal precursors, Fe2+, Cu+, Ni2+ and Zn2+ led to the isolation of complexes X4.23 (PNNNP, Ni2+), X4.24 (NNNP, Fe2+), X2.25 (PNNNP, Fe2+) X4.26 (ONNNO, Fe2+), X4.27 (PP, Cu+) and X4.29 (NNNP, Zn2+), which were all characterised by X-ray crystallography. 2024-07-24 Thesis (University of Nottingham only) NonPeerReviewed application/pdf en cc_by https://eprints.nottingham.ac.uk/77946/1/Olivia%20Churchill%20%5B20101928%5D%20Synthesis%20and%20Complexation%20of%20a%20Bulky%20Silyl%20Phosphanide%20and%20Extended%20PNNNP%20Carbazole-based%20Ligand.pdf Churchill, Olivia (2024) Synthesis and Complexation of a Bulky Silyl Phosphanide and Extended PNNNP Carbazole-based Ligand. PhD thesis, University of Nottingham. phosphanide ligands synthesis
spellingShingle phosphanide
ligands
synthesis
Churchill, Olivia
Synthesis and Complexation of a Bulky Silyl Phosphanide and Extended PNNNP Carbazole-based Ligand
title Synthesis and Complexation of a Bulky Silyl Phosphanide and Extended PNNNP Carbazole-based Ligand
title_full Synthesis and Complexation of a Bulky Silyl Phosphanide and Extended PNNNP Carbazole-based Ligand
title_fullStr Synthesis and Complexation of a Bulky Silyl Phosphanide and Extended PNNNP Carbazole-based Ligand
title_full_unstemmed Synthesis and Complexation of a Bulky Silyl Phosphanide and Extended PNNNP Carbazole-based Ligand
title_short Synthesis and Complexation of a Bulky Silyl Phosphanide and Extended PNNNP Carbazole-based Ligand
title_sort synthesis and complexation of a bulky silyl phosphanide and extended pnnnp carbazole-based ligand
topic phosphanide
ligands
synthesis
url https://eprints.nottingham.ac.uk/77946/