Churchill, Olivia
(2024)
Synthesis and Complexation of a Bulky Silyl Phosphanide and Extended PNNNP Carbazole-based Ligand.
PhD thesis, University of Nottingham.
Abstract
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.
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