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Divalent iron, cobalt, nickel and palladium complexes of 1H-pyrazol-1-yl-imine and 1H-pyrazol-1-yl-ethanol ligands: coordination chemistry and evaluation as ethylene oligomerization catalysts

M.Sc. / This dissertation deals with the syntheses of tridentate (O^N^N) coordination ligands [{2,4-di-tert-butyl-6-[(2-(3,5-RR-pyrazol-1-yl-ethylimino)-methyl] phenol}, R = H (L1), Me(L2), Ph(L3), t-Bu(L4)], which was reacted initially with MX2 (M = Fe, Co, Ni; X = Cl, Br). The ligands L1-L4 were also modified by functionalizing the phenol group in this ligand group to an ethoxy in L5 and L6 (L5 = [(3,5-di-tert-butyl-2-ethoxy-benzylidene)-[2-(3,5-dimethyl-pyrazol-1-yl)-ethyl]-amine, L6 = [(3,5-di-tert-butyl-2-ethoxy-benzylidene)-[2-(3,5-di-tert-butyl-pyrazol-1-yl)-ethyl]-amine)], or into a phenoxy in L7 (L7 = (3,5-di-tert-butyl-2-phenoxy-benzylidene-(2-pyrazol-1-yl-ethyl)-amine)). Another ligand L8 (L8 = [4-(4-tert-butyl-benzylidene)-[2-(3,5-dimethyl-pyrazol-1-yl)-ethyl]-amine], which was devoid of the phenoxy group was also synthesized. These modified ligands were also reacted with MX2 or PdCl(COD)Me to form bidentate (N^N) chelating complexes. Further modification of the ligand L1-L4, to replace the phenoxy pyrazolylimine unit with a source of oxygen donor other than a phenoxy led to the use of already known ligands L9, L10 (L9 = 2-(3,5-dimethyl-pyrazol-1-yl)-ethanol, L10 = 2-(3,5-di-tert-butyl-pyrazol-1yl)-ethanol and L11, where in L11, the alcohol moiety is replaced by an electron withdrawing chloro group, L11 = 1-(2-chloroethyl)-3,5-di-methyl-pyrazole). These ligands were also reacted with MX2 (M = Fe, Co, Ni, Pd; X = Cl, Br) to form complexes. The synthesized complexes were characterized by a combination of IR and NMR spectroscopy, mass spectrometry, microanalysis and in selected cases single crystal X-ray crystallography.

Identiferoai:union.ndltd.org:netd.ac.za/oai:union.ndltd.org:uj/uj:7079
Date16 May 2011
Source SetsSouth African National ETD Portal
Detected LanguageEnglish
TypeThesis

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