Graduation date: 1997

M.Sc. (Chemistry) / This study deals with the synthesis of nitrogen-donor pyrazole- and pyrazolylethylamine compounds, their reactions with palladium(II) and nickel(II) precursors to form complexes and the applications of theses palladium(II) and nickel(II) complexes as catalysts for ethylene oligomerization reactions and reactions of higher α-olefins in Friedel-Crafts alkylation of aromatic solvents. A series of ligands, 3,5-di-tert-butyl-1H-pyrazole (L3), 3,5-diphenyl-1H-pyrazole (L4), 5-phenyl-3-(trifluoromethyl)-1H-pyrazole (L5) were synthesized using appropriate amounts of diketones and hydrazine hydrate; while ligands, 2-(1H-pyrazol-1-yl)ethylamine (L6), 2-(3,5-dimethyl-1H-pyrazol-1-yl)-ethylamine (L7), 2-(3,5-di-tert-butyl-1H-pyrazol-1-yl)-ethylamine (L8), 2-(3,5-diphenyl-1H-pyrazol-1-yl)-ethylamine (L9) and 2-(5-phenyl-3-(trifluoromethyl)-1H-pyrazol-1-yl)ethylamine (L10) were prepared via the N sp3 alkylation of the corresponding pyrazoles with bromoethylamine Reactions of L1-L5 with [PdCl2(CNMe)2] formed five complexes of general formula [PdCl2 (L)2] {L = L1 (2.1), L2 (2.2), L3 (2.3), L4 (2.4) and L5 (2.5)}. Similarly [NiBr2(DME)] formed five complexes of general formula [NiBr2(L)2] {L = L1(2.6), L2 (2.7), L3 (2.8), L4 (2.9) and L5 (2.10)}. Complexes 2.1-2.10 were synthesized in a 2:1 mole ratio of ligand and metal precursor. Reactions of L6-L10 with [PdCl2(MeCN)2] yielded complexes 3.1-3.5 respectively. Ligands L6-L10 were also complexed with NiCl2.6H2O to give complex 3.6 while [NiCl2(DME)] and [NiBr2(DME)] gave complexes 3.7-3.8 and 3.9-3.13 respectively...

M.Sc. / This study describes the synthesis of pyrazolyl palladium and nickel complexes and their applications as catalysts for the co-polymerization of olefins with carbon monoxide and also as ethylene oligomerization catalysts. A series of compounds, 2-(3,5-dimethyl-pyrazol-1-yl)-ethyl]-pyridin-2-ylmethylene-imine (L1), 2-(3,5-di-tert-butyl-pyrazol-1-yl)-ethyl]-pyridin-2-ylmethylene-imine (L2), 2-(3,5-dimethyl-pyrazol-1-yl)-ethyl]-thiophen-2-ylmethylene-imine (L3), 2-(3,5-di-tert-butyl-pyrazol-1-yl)-ethyl]-thiphen-2-ylmethylene-imine (L4), 2-(3,5-dimethyl-pyrazol-1-yl)-ethyl]-5-bromothiophen-2-ylmethylene-imine (L5), 2-(3,5-di-tert-butyl-pyrazol-1-yl)-ethyl]-2bromothiophen-2-ylmethylene-imine (L6), 2-(3,5-dimethyl-pyrazol-1-yl)-ethyl]-pyrrol-2-ylmethylene-imine (L7) and 2-(3,5-di-tert-butyl-pyrazol-1-yl)-ethyl]-pyrrol-2-ylmethylene-imine (L8)] were prepared via Schiff base condensation of the appropriate amines and aldehydes. Reactions of L1-L6 and L8 with [PdClCH3(cod)] formed six complexes of general formula [PdClCH3(L)] {L = L1 (1), L2 (2), L3 (3), L4 (4), L5 (5) and L6 (6)} and [Pd(L8)2] (7). Complexes 1-6 were converted to the cationic compounds [PdCH3(L)]BAr4 {L = L1 (8), L2 (9), L3 (10), L4 (11), L5 (12) and L6 (13)} by the reaction of compounds 1-6 with the halide abstractor Na[BAr4] (where Ar = (3,5-(CF3)2C6H3) in a 1:1 mole ratio. For compounds 8 and 9 the cationic species were stabilized by the coordination of the pyrazolyl units of the ligands, which were uncoordinated in the parent palladium complexes 1 and 2. The cationic complexes 10-13, however, were stabilized by v coordination of NCCH3 to the palladium centre. Complexation of L1, L2, L5 and L6 with [PdCl2(NCCH3)2] gave the palladium dichloro complexes [PdCl2(L)], {L = L1 (14), L2 (15), L5 (16), and L6 (17)}. Compounds L1, L2, L7 and L8 were reduced to form compounds L9-L12 respectively and were reacted with [NiBr2DME] to form complexes [NiBr2(L)] {L = L9 (18), L10 (19), L11 (20) and L12 (21).