Synthetic, equilibrium, kinetic and mechanistic studies of the reactions between azo dye ligands and Ni²+

Doctoral thesis English OPEN
Blount, Jay Adam
  • Subject: QD

12 azo dye ligands LI-LI2 that are used in the inkjet printer industry have been synthesised\ud and characterised. The dyes L5B and L3765 were supplied as gifts by the chemical\ud company Avecia. All dyes were fully examined by IH NMR, 13e NMR, IR spectroscopy,\ud electrospray mass spectroscopy, atomic absorption spectroscopy, UV-Visible spectroscopy\ud and microanalyses. Melting points were also determined.\ud pKa values have been determined by visible spectroscopy for the dyes\ud PAN(Aldrich), L7, L3765, Ll, L5 and L5B. Stability constant measurements have been\ud attempted for the Ni(II) complexes of PAN, LI and L5 using UV-Visible spectroscopy.\ud Single wavelength stopped-flow kinetic studies of the reactions of Ni(II) with\ud PAN(Aldrich), PADA(Aldrich), SUDAN I(Aldrich), L3765 and L7 were carried out.\ud Multi wavelength stopped-flow kinetic studies of the reactions of Ni(II) with\ud L 1, L 7, L5 and L5B were examined and rate constants for complex formation (kf ) were\ud determined. Rates of dissociation of [Ni(PAN)2] using ligand exchange with either EDTA\ud or 2,2' :6' ,2" -Terpyridine (Terpy) were investigated using UV -Visible spectroscopy.\ud Relative stabilities of [Ni(II)(PAN)t, [Ni(II)(L 7)] and [Ni(II)(L3765)r have been\ud determined. Dissociation of Ni(II) complexes of Ll, L5, L5B, L6, PAN, L7 and L3765\ud using excess Terpy have been studied using UV -Visible spectroscopy and relative\ud stabilities have been compared.\ud
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